Herbicidal benzodioxoles and benzodioxanes

ABSTRACT

Compounds of Formula I, and their N-oxides and agriculturally-suitable salts, are disclosed which are useful for controlling undesired vegetation ##STR1## wherein: ##STR2## T is O or S; W is a single bond, O, S or NR 6  ; 
     X is N or CH; 
     Y is N or CH; 
     Z is N or CR 7  provided that when Z is CR 7 , then Y is N; 
     R 6  is H, CH 3  or OCH 3  ; 
     m is 1 or 2; and 
     R 1 , R 2 , R 3 , R 4 , R 5 , and R 7  are as defined in the disclosure. 
     Also disclosed are compositions containing the compounds of Formula I and a method for controlling undesired vegetation which involves contacting the vegetation or its environment with an effective amount of a compound of Formula I.

BACKGROUND OF THE INVENTION

This invention relates to certain benzodioxoles and benzodioxanes, theirN-oxides, agriculturally-suitable salts and compositions, and methods oftheir use for controlling undesirable vegetation.

WO 93/11097 discloses anilides of Formula i as herbicides: ##STR3##wherein Q is, among others, Q-1 ##STR4## R is, among others, C₁ -C₂haloalkyl, C₁ -C₂ haloalkoxy, C₁ -C₂ haloalkylthio, halogen, cyano, ornitro;

Y is NR⁷ C(O)XR³ ;

X is a single bond, O, S or NR⁴ ;

R¹ is, among others, H, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃ alkylthio,C₂ -C₃ alkoxyalkyl, C₂ -C₃ alkylthioalkyl, halogen, NO₂, CN, NHR⁵ or NR⁵R⁶ ; and

R³ is, among others, C₁ -C₅ alkyl optionally substituted with C₁ -C₂alkoxy, OH, 1-3 halogens, or C₁ -C₂ alkylthio; CH₂ (C₃ -C₄ cycloalkyl);C₃ -C₄ cycloalkyl optionally substituted with 1-3 CH₃ 's; C₂ -C₄alkenyl; or C₂ -C₄ haloalkenyl.

U.S. Pat. No. 5,389,600 discloses heterocycles of Formula ii asherbicides: ##STR5## wherein X is N or CH;

Y is N or CR⁸ ;

Z is N, CR⁴ or CR⁵ ;

Q is N, CR⁴ or CR⁵ ;

R is C₁ -C₄ alkyl, C₂ -C₄ alkoxyalkyl, C₂ -C₄ alkenyl, C₂ -C₄ alkynyl,C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₃ alkylamino or N(C₁ -C₃ alkyl)(C₁-C₃ alkyl);

R¹ is H, F, Cl or CH₃ ;

R² is H, halogen, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, C₁ -C₃ alkoxy or C₁-C₃ haloalkoxy;

R³ is H, halogen, C₁ -C₄ alkyl, C₂ -C₄ alkenyl, C₂ -C₄ alkynyl, C₁ -C₄haloalkyl, C₃ -C₄ halocycloalkyl, C₂ -C₄ haloalkenyl, C₂ -C₄haloalkynyl, OR⁶, S(O)_(n) R⁷ or CN;

R⁴ is H, CN, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or halogen;

R⁵ is C₁ -C₄ haloalkyl, C₃ -C₅ halocycloalkyl, C₂ -C₄ haloalkenyl, C₂-C₄ haloalkynyl, OR⁶, S(O)_(n) R⁷ or halogen;

R⁶ is C₁ -C₄ alkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, C₁ -C₄ haloalkyl, C₂-C₄ haloalkenyl or C₂ -C₄ haloalkynyl;

R⁷ is C₁ -C₂ alkyl or C₁ -C₂ haloalkyl;

R⁸ is H, CN, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or halogen; and

n is 0, 1 or 2.

WO 94/21640 discloses benzodioxoles of Formula iii as herbicides:##STR6## wherein R₁ is H, C₁ -C₄ alkyl or C₁ -C₄ haloalkyl; and

R₂ is C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C_(1-C) ₄haloalkoxy, C₁ -C₄ alkylthio, C₁ -C₄ haloalkylthio, C₁ -C₄ alkoxy-C₁ -C₄alkyl, C₁ -C₄ alkoxy-C₁ -C₄ alkoxy, C₁ -C₄ alkoxy-C₁ -C₄ alkylthio,halogen, amino, C₁ -C₄ alkylamino or C₁ -C₄ dialkylamino.

The benzodioxoles and benzodioxanes of the present invention are notdisclosed in any of these references.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula I including allgeometric and stereoisomers, N-oxides, and agriculturally suitable saltsthereof, agricultural compositions containing them and their use forcontrolling undesirable vegetation: ##STR7## wherein Q is ##STR8## T isO or S; W is a single bond, O, S or NR⁶ ;

X is N or CH;

Y is N or CH;

Z is N or CR⁷ provided that when Z is CR⁷, then Y is N;

R¹ is C₁ -C₅ alkyl optionally substituted with C₁ -C₂ alkoxy, OH, 1-3halogens, or C₁ -C₂ alkylthio; CH₂ (C₃ -C₄ cycloalkyl); C₃ -C₄cycloalkyl optionally substituted with 1-3 methyl groups; C₂ -C₄alkenyl; C₂ -C₄ haloalkenyl; or phenyl optionally substituted withhalogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy, nitro or cyano;

R² is H, chlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, C₁ -C₂alkylthio, C₂ -C₃ alkoxyalkyl, C₂ -C₃ alkylthioalkyl, cyano, nitro,NH(C₁ -C₂ alkyl) or N(C₁ -C₂ alkyl)₂ ;

R³ is C₁ -C₄ alkyl, C₂ -C₄ alkoxyalkyl, C₂ -C₄ alkenyl, C₂ -C₄ alkynyl,C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₃ alkylamino or N(C₁ -C₃ alkyl)(C₁-C₃ alkyl);

R⁴ is H or F;

R⁵ is H, CN, C₁ -C₃ alkyl, C₁ -C₄ haloalkyl, C₃ -C₄ halocycloalkyl, C₂-C₄ haloalkenyl, C₃ -C₄ haloalkynyl, OR⁸, S(O)_(n) R⁹ or halogen;

R⁶ is H, CH₃ or OCH₃ ;

R⁷ is H, CN, C₁ -C₃ alkyl, C₁ -C₄ haloalkyl, C₃ -C₄ halocycloalkyl, C₂-C₄ haloalkenyl, C₃ -C₄ haloalkynyl, OR¹⁰, S(O)_(p) R¹¹ or halogen;

R⁸ and R¹⁰ are each independently C₁ -C₄ alkyl, C₃ -C₄ alkenyl, C₃ -C₄alkynyl, C₁ -C₄ haloalkyl, C₂ -C₄ haloalkenyl or C₃ -C₄ haloalkynyl;

R⁹ and R¹¹ are each independently C₁ -C₂ alkyl or C₁ -C₂ haloalkyl;

m is 1 or 2; and

n and p are each independently 0, 1 or 2;

provided that when Z is CR⁷, then exactly one of R⁵ and R⁷ is H.

In the above recitations, the term "alkyl", used either alone or incompound words such as "alkylthio" or "haloalkyl" includesstraight-chain or branched alkyl, such as, methyl, ethyl, n-propyl,i-propyl, or the different butyl or pentyl isomers. "Alkenyl" includesstraight-chain or branched alkenes such as vinyl, 1-propenyl,2-propenyl, and the different butenyl isomers. "Alkenyl" also includespolyenes such as 1,3-butadienyl. "Alkynyl" includes straight-chain orbranched alkynes such as ethynyl, 1-propynyl, 3-propynyl and thedifferent butynyl isomers. "Alkynyl" can also include moieties comprisedof multiple triple bonds such as 1,3-butadiynyl. "Alkoxy" includes, forexample, methoxy, ethoxy, n-propyloxy, isopropyloxy and the differentbutoxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl.Examples of "alkoxyalkyl" include CH₃ OCH₂, CH₃ OCH₂ CH₂, CH₃ CH₂ OCH₂,CH₃ CH₂ CH₂ OCH₂ and CH₃ CH₂ OCH₂ CH₂. "Alkylthio" includes branched orstraight-chain alkylthio moieties such as methylthio, ethylthio, and thedifferent propylthio and butylthio isomers. "Alkylamino", and the like,are defined analogously to the above examples. "Cycloalkyl" includes,for example, cyclopropyl and cyclobutyl.

The term "halogen", either alone or in compound words such as"haloalkyl", includes fluorine, chlorine, bromine or iodine. The term"1-3 halogen" indicates that one, two or three of the availablepositions for that substituent may be halogen. Further, when used incompound words such as "haloalkyl", said alkyl may be partially or fullysubstituted with halogen atoms which may be the same or different.Examples of "haloalkyl" include F₃ C, ClCH₂, CF₃ CH₂ and CF₃ CCl₂. Theterms "haloalkenyl", "haloalkynyl" "haloalkoxy", and the like aredefined analogously to the term "haloalkyl". Examples of "haloalkenyl"include (Cl)₂ C═CHCH₂ and CF₃ CH═CHCH₂. Examples of "haloalkynyl"include HC.tbd.CCHCl, CF₃ C.tbd.C, CCl₃ C.tbd.C and FCH₂ C.tbd.CCH₂.Examples of "haloalkoxy" include CF₃ O, CCl₃ CH2O, HCF₂ CH₂ CH₂ O andCF₃ CH₂ O.

The total number of carbon atoms in a substituent group is indicated bythe "C_(i) -C_(j) " prefix where i and j are numbers from 1 to 5. Forexample, C₁ -C₃ alkylthio designates methylthio through propylthio; C₂alkoxyalkyl designates CH₃ OCH₂ ; C₃ alkoxyalkyl designates, forexample, CH₃ CH(OCH₃), CH₃ OCH₂ CH₂ or CH₃ CH₂ OCH₂ ; and C₄ alkoxyalkyldesignates the various isomers of an alkyl group substituted with analkoxy group containing a total of four carbon atoms, examples includingCH₃ CH₂ CH₂ OCH₂, and CH₃ CH₂ OCH₂ CH₂.

When a group contains a substituent which can be hydrogen, for exampleR² or R⁵, then, when this substituent is taken as hydrogen, it isrecognized that this is equivalent to said group being unsubstituted.

Compounds of this invention can exist as one or more stereoisomers. Thevarious stereoisomers include enantiomers, diastereomers, atropisomersand geometric isomers. One skilled in the art will appreciate that onestereoisomer may be more active and/or may exhibit beneficial effectswhen enriched relative to the other stereoisomer(s) or when separatedfrom the other stereoisomer(s). Additionally, the skilled artisan knowshow to separate and/or to selectively prepare said stereoisomers.Accordingly, the present invention comprises compounds selected fromFormula I, N-oxides and agriculturally suitable salts thereof. Thecompounds of the invention may be present as a mixture of stereoisomers,individual stereoisomers, or as an optically active form.

The salts of the compounds of the invention include acid-addition saltswith inorganic or organic acids such as hydrobromic, hydrochloric,nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic,malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic orvaleric acids. The salts of the compounds of the invention also includethose formed with organic bases (e.g., pyridine, ammonia, ortriethylamine) or inorganic bases (e.g., hydrides, hydroxides, orcarbonates of sodium, potassium, lithium, calcium, magnesium or barium)when the compound contains an acidic group.

Preferred compounds for reasons of better activity and/or ease ofsynthesis are: agriculturally-suitable salts thereof, wherein:

R¹ is C₁ -C₄ alkyl optionally substituted with methoxy or 1-3 halogens;C₂ -C₄ alkenyl; or C₂ -C₄ haloalkenyl;

R² is chlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, cyano, nitro,NH(C₁ -C₂ alkyl) or N(C₁ -C₂ alkyl)₂ ; and

R³ is C₁ -C₃ alkyl, C₂ -C₃ alkoxyalkyl, C₂ -C₃ alkenyl, C₂ -C₃ alkynyl,C₁ -C₂ alkoxy, C₁ -C₂ alkylthio, C₁ -C₂ alkylamino or N(C₁ -C₂ alkyl)(C₁-C₂ alkyl);

R⁷ is H, C₁ -C₂ haloalkyl, OR¹⁰, or S(O)_(p) R¹¹ ;

R¹⁰ is C₁ -C₂ haloalkyl;

R¹¹ is C₁ haloalkyl; and

p is 0.

Preferred 2. Compounds of Preferred 1 wherein:

T is O;

W is a single bond;

m is 1; and

n is 0.

Preferred 3. Compounds of Preferred 2 wherein:

R⁵ is H, C₁ -C₂ haloalkyl, OR⁸, or SR⁹ ;

R⁷ is H, CF₃, or OR¹⁰ ;

R⁸ is C₁ -C₂ haloalkyl;

R⁹ is C₁ haloalkyl; and

R¹⁰ is CF₂ H.

Most preferred are compounds of Preferred 3 selected from the group:

N-[2-(2,2-difluoro-1,3-benzodioxol-4-yl)-4-methylphenyl]-2-methylpropanamide;and

8-(2,2-difluoro-1,3-benzodioxol-4-yl)-2-(difluoromethoxy)-6-methylquinoxaline.

This invention also relates to herbicidal compositions comprisingherbicidally effective amounts of the compounds of Formula I and atleast one of a surfactant, a solid diluent or a liquid diluent. Thepreferred compositions of the present invention are those which comprisethe above preferred compounds.

This invention also relates to a method for controlling undesiredvegetation comprising applying to the locus of the vegetationherbicidally effective amounts of the compounds of Formula I and thecompositions described herein. The preferred methods of use are thoseinvolving the above preferred compounds.

DETAILS OF THE INVENTION

The compounds of Formula I can be prepared by one or more of thefollowing methods and variations as described in Schemes 1-9. Thedefinitions of Q, T, W, X, Y, Z, R¹ through R¹¹, m, n, and p in thecompounds of Formulae I-VIII below are as defined above in the Summaryof the Invention. Compounds of Formulae Ia and Ib are various subsets ofthe compounds of Formula I, and all substituents for Formulae Ia and Ibare as defined above for Formula I. ##STR9##

Scheme 1 illustrates the preparation of compounds of Formula I wherebyaromatic compounds of Formula II wherein G is chlorine, bromine, iodine,or trifluoromethylsulfonyloxy (OTf) can be coupled with substitutedphenyl compounds of Formula III wherein J is a trialkyltin (e.g., Me₃Sn), trialkylsilyl (e.g., Me₃ Si), halometal (e.g., ZnCl, MgBr, CuCl, orHgCl), or boronic acid (e.g., B(OH)₂) moiety. The coupling is carriedout using methods known in the art: Tsuji, J. Organic Synthesis withPalladium Compounds; Springer-Verlag: Berlin, 1980; Negishi, E. Acc.Chem. Res. (1982), 15, 340; Stille, J. K. Angew. Chem. (1986), 98, 504;Yamamoto, A., Yamagi, A. Chem. Pharm. Bull. (1982), 30, 1731 and 2003;Dondoni, A., Fogagnolo, M., Medici, A., Negrini, E. Synthesis (1987),185; Dondoni, A., Fantin, G., Fogagnolo, M., Medici, A., Pedrini, P.Synthesis (1987), 693; Hoshino, Y., Miyaura, N., Suzuki, A. Bull Chem.Soc. Jpn. (1988), 61, 3008; Sato, M., Miyaura, N., Suzuki, A. Chem. Lett(1989), 1405; Mayaura, N., Yanagi, T., Suzuki, A. Synth. Commun. (1981),11, 513; Siddiqui, M. A., Snieckus, V. Tetrahedron Lett. (1988), 29,5463; Sharp, M. J., Cheng, W., Snieckus, V. Tetrahedron Lett. (1987),28, 5093; Hatanaka, Y., Fukushima, S., Hiyama, T. Chem. Lett. (1989),1711; Bailey, T. R. Tetrahedron Lett. (1986), 27, 4407; Echavarren, A.M., Stille, J. K. J. Am. Chem. Soc. (1987), 109, 5478; Ali et al.,Tetrahedron Lett. (1992), 48, 8117; Negishi, E., Takahashi, T., King, A.Org. Synth (1987), 66, 67; Negishi, E., King, A., Okukado, N. J. Org.Chem. (1977), 42, 1821; and Minato, A., Tamao, K., Huyashi, T., Suzuki,K., Kumada, M. Tetrahedron Lett. (1980), 21, 845.

The coupling of lI and III is carried out in the presence of atransition metal catalyst such as tetrakis(triphenylphosphine) palladium(0) or bis(triphenylphosphine) palladium (II) dichloride in a solventsuch as toluene, acetonitrile, tetrahydrofuran, or ethylene glycoldimethyl ether and optionally in the presence of an aqueous inorganicbase such as sodium hydrogen carbonate or an organic base such astriethylamine. As shown in Scheme 1, compounds of Formula I can also beprepared by coupling aromatic compounds of Formula IV wherein J is atrialkyltin (e.g., Me₃ Sn), trialkylsilyl (e.g., Me₃ Si), halometal(e.g., ZnCl, MgBr, CuCl, or HgCl), or boronic acid (e.g., B(OH)₂) moietywith substituted phenyl compounds of Formula V wherein G is chlorine,bromine, iodine, or trifluoromethylsulfonyloxy (OTf). Compounds ofFormula III and V are known in the art. (For m=1, see EP 333,658, andfor m=2, see DE 3223505.) The procedure for conducting the coupling isthe same as those described and referenced above. ##STR10##

By methods also reported in the above cited art, treatment of compoundsof Formulae II and V wherein G is hydrogen, bromine or iodine with ametalating agent such as n-butyllithium followed by quenching with atrialkyltin halide, trialkylsilyl halide, metal halide, or trialkylborate produces intermediates of Formulae III and IV.

Heterocycles of Formula IIb are either known or are readily prepared byprocedures and techniques well known in the art, e.g., U.S. Pat. No.5,389,600 and references therein. ##STR11##

In addition, Scheme 2 illustrates the regioselective syntheses ofquinoxalines and pyridopyrazines of Formulae VIf and VIg by proceduresknown in the art, for example: Tenant, G. J. Chem. Soc. (1963),2428-2433 and Ahead, Y. et al. Tetrahedron (1965), 21, 861-865.Derivatives of o-nitroacetanilide containing an activated methylenegroup cyclize in the presence of aqueous base giving compounds ofFormula VIc or VId depending on reaction conditions.

Compounds of Formulae VIc and VId can then be reduced to quinoxalinesand pyridopyrazines of Formulae VIf and VIg, respectively. N-oxides ofFormula VIc can be converted into dihydroxy quinoxalines andpyridopyrazines of Formula VIe. Acid chloride and methyl ester analogsof VIa can also be used in this sequence. ##STR12##

Anilines of Formula VIIb are readily prepared by palladium catalyzedcoupling of an ortho-substituted nitrophenyl compound of Formula VII,wherein G is as defined above, with a substituted phenyl compound ofFormula III wherein J is as defined above, followed by catalytic orchemical reduction of the nitro group (Scheme 3). Alternatively, thereactivity of the substrates can be reversed; i.e., the coupling iscarried out using an ortho-substituted nitrophenyl compound of FormulaVIIc and a substituted phenyl compound of Formula V where G and J are asdefined above. The procedure for conducting the coupling is the same asthose described and referenced above.

Reduction of nitro groups to amino groups is well documented in thechemical literature. See for example, Ohme, R. and Zubek, A. R. andZubek, A. in Preparative Organic Chemistry; Hilgetag, G. and Martini,A., Eds.; John Wiley & Sons, New York, 1972, p 557. ##STR13##

In some cases it is desirable to perform the palladium coupling reactionon an N-protected form of the aniline, for example the2,2-dimethylpropanamide. Upon completion of the coupling reaction, theN-protecting group can be removed, for example by treatment of the2,2-dimethylpropanamide with acid, to liberate the amino group.

Compounds of Formula Ia can be prepared by one skilled in the art fromanilines of Formula VIIb by treatment with an appropriate acyl chlorideor acid arthydride (T═O, W═direct bond), chloroformate (T═O, W═O),chlorothiolformate (T═O, W═S), carbamoyl chloride (T═O, W═NR⁶),isothiocyanate (T═S, W═NH), isocyanate (T═O, W═NH), or xanthyl chloride(T═S, W═S), under conditions well known in the literature, for example:Sandler, R. S. and Karo, W. Organic Functional Group Preparations, 2nded.; Academic: New York, Vol. I, p 274 and Vol. II, pp 152, 260 (Scheme4). ##STR14##

Anilines of Formula VIIb can also be converted into the correspondingisocyanate by treatment with phosgene or known phosgene equivalents(e.g. ClC(═O)OCCl₃), and then condensed with an appropriate alcohol oramine of Formula VIII to afford anilides of Formula Ia (Scheme 5). Thesetechniques are well known in the literature, for example: Sandler, R. S.and Karo, W. Organic Functional Group Preparations, 2nd ed.; Academic:New York, Vol. II, pp 152, 260; Lehman, G. and Teichman, H. inPreparative Organic Chemistry, 472, Hilgetag, G. and Martini, A., Eds.,John Wiley & Sons: New York, 1972; Eckert, H. and Forster, B. Angew.Chem. Int. Ed. in Engl., (1987), 26, 894; Babad, H. and Zeiler, A. G.Chem. Rev. (1973), 73, 75. ##STR15##

As shown in Scheme 6, compounds of Formula Ia where T═S can be preparedfrom compounds of Formula Ia where T═O by treatment with P₂ S₅ orLawesson's reagent(2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide)under conditions well known in the literature, for example: T. P.Sychera et at., J. Heterocycl. Chem. (1989), 26, 1039-1043; E. C. TaylorJr. et al., J. Am. Chem. Soc. (1953), 75, 1904; and O. P. Goel et al.,Synthesis-Stuttgart (1987), 2, 162-164. ##STR16##

Anilines of Formula VIIb can also be converted into the correspondingisothiocyanate by treatment with thiophosgene or known thiophosgeneequivalents (e.g. 1,1'-thiocarbonyldiimidazole) and then condensed withan appropriate alcohol or amine of Formula VIIIa or a Grignard reagentto afford compounds of Formula Ia where T═S (Scheme 7). ##STR17##

Variation of the substituent R² on the anilide Q-2 of compounds ofFormula Ia may be achieved in one of two ways. First, one skilled in theart may simply select the appropriate aromatic compound of Formula IIaor IV for the palladium coupling in Scheme 1 to give examples with avariety of values for R². In some instances it may be necessary or moreconvenient to introduce the desired substituents after the couplingreaction was performed. This can be accomplished by electrophilicsubstitution (Scheme 8) or nucleophilic substitution on compounds ofFormula VIIa and/or various functional group transformations (Scheme 9).Methods to perform these transformations are well known in theliterature. Some examples include conversion of chloro to bromo (L. J.Street et al., J. Med. Chem. (1992), 35, 295-304), bromo to cyano (G. P.Ellis, T. M. Romney-Alexander Chem. Rev. (1987), 87, 779-794), bromo toalkoxy and alkylthio, and amino to a variety of substituents via thediazonium salts. Appropriately substituted compounds of Formula VIIawould then be reduced to amino compounds of Formula VIIb usingconditions previously discussed. ##STR18##

It is recognized that some reagents and reaction conditions describedabove for preparing compounds of Formula I may not be compatible withcertain functionalities present in the intermediates. In theseinstances, the incorporation of protection/deprotection sequences orfunctional group interconversions into the synthesis will aid inobtaining the desired products. The use and choice of the protectinggroups will be apparent to one skilled in chemical synthesis (see, forexample, Greene, T. W.; Wuts, P. G. M. Protective Groups in OrganicSynthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art willrecognize that, in some cases, after the introduction of a given reagentas it is depicted in any individual scheme, it may be necessary toperform additional routine synthetic steps not described in detail tocomplete the synthesis of compounds of Formula I.

One skilled in the art will also recognize that compounds of Formula Iand the intermediates described herein can be subjected to variouselectrophilic, nucleophilic, radical, organometallic, oxidation, andreduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the artusing the preceding description can utilize the present invention to itsfullest extent. The following Examples are, therefore, to be construedas merely illustrative, and not limiting of the disclosure in any waywhatsoever. Percentages are by weight unless otherwise indicated. Partsfor chromatographic solvent mixtures are by volume unless otherwiseindicated. ¹ H NMR spectra are reported in ppm downfield fromtetramethylsilane; s=singlet, d=doublet, t=triplet, m=multiplet, brs=broad singlet.

EXAMPLE 1

Step A: Preparation of 2-bromo-4-methyl-6-nitrobenzenamine

A solution of bromine (23.24 mL, 453.5 mmol) in glacial acetic acid (50mL) was added dropwise over 2 h to a mechanically-stirred suspension of4-methyl-2-nitroaniline (60.00 g, 394.3 mmol) in glacial acetic acid(200 mL) at room temperature under a nitrogen atmosphere. The mixturewas stirred at room temperature 1 h, and then most of the acetic acidwas removed under reduced pressure. The resultant orange solid wasdissolved in a mixture of saturated aqueous sodium bicarbonate (1500 mL)and ethyl acetate (500 mL). The layers were separated and the aqueoussolution was again extracted with ethyl acetate. The combined organiclayers were washed once with water, dried (MgSO₄), filtered, andconcentrated under reduced pressure to afford the title compound of StepA as an orange solid melting at 64°-65.5° C. (89.694 g, 98%). ¹ H NMR(CDCl₃): δ2.28 (s,3H), 6.45 (br s,2H), 7.55 (s, 1H), 7.94 (s, 1H).

Step B: Preparation ofN-(2-bromo-4-methyl-6-nitrophenyl)-3-oxobutanamide

A solution of diketene (57.71 mL, 748.2 mmol) was added dropwise over 2h to a stirred solution of title compound of Step A (34.57 g, 149.6mmol) and 4-dimethylaminopyridine (914 mg, 7.48 mmol) in drytetrahydrofuran (450 mL) at room temperature under a nitrogenatmosphere. The reaction was allowed to stir at room temperatureovernight. First, water was added to the reaction, and then the reactionmixture was poured into water. The mixture was saturated with sodiumchloride and was extracted with ethyl acetate three times. The combinedorganic layers were dried (MgSO₄), filtered, and the solvent was removedunder reduced pressure to give a brown oil. The brown oil was suspendedin 1-chlorobutane. The resultant precipitate was filtered from thissuspension to afford the title compound of Step B as a brown solidmelting at 136°-138° C. (21.67 g, 46%). ¹ H NMR (CDCl₃): δ2.35 (s,3H),2.41 (s,3H), 3.63 (s,2H), 7.69 (s,2H), 9.6 (br s, 1H).

Step C: Preparation of 8-bromo-6-methyl-2-quinoxalinol 4-oxide

The title compound of Step B (11.75 g, 37.29 mmol) was suspended in amixture of isopropanol (120 mL) and water (120 mL) at room temperatureunder a nitrogen atmosphere. A solution of sodium hydroxide (14.91 g ofa 50% aqueous solution, 186.4 mmol) diluted with water (10 mL) was addeddropwise to the mixture over 30 min. The mixture was allowed to stir atroom temperature overnight. First, 1N hydrochloric acid and thenconcentrated hydrochloric acid were added dropwise to the reactionmixture until the pH was approximately 2. Solids were filtered from thereaction mixture. These solids were washed with water and then coldethyl acetate to afford the title compound of Step C as a reddish-brownsolid melting at 241°-243° C. (8.67 g, 91%). ¹ H NMR ((CD₃)₂ SO): δ2.47(s,3H), 7.69 (s, 1H), 7.81 (s, 1H), 8.12 (s, 1H), 8.9 (br s, 1H).

Step D: Preparation of 8-bromo-6-methyl-2-quinoxalinol

The title compound of Step C (25 g, 98 mmol) and sodium dithionite (38g, 220 mmol) were suspended in a mixture of ethanol (1000 mL) and water(200 mL) at room temperature. After 1 h, most of the solvent was removedunder reduced pressure. The residue was diluted with water and acidifiedwith hydrochloric acid. Insolubles were removed by filtration. Thefiltrate was extracted twice with methylene chloride. The combinedorganic extracts were dried (MgSO₄), filtered, and concentrated underreduced pressure to afford the title compound of Step D as a tan/yellowsolid (15.29 g, 65%). ¹ H NMR (CDCl₃): δ2.37 (s,3H), 7.5 (d,2H), 8.15(s, 1H), 9.8 (br s, 1H).

Step E: Preparation of 8-bromo-2-(difluoromethoxy)-6-methylquinoxaline

Tetrabutylammonium bromide (689 mg, 2.14 mmol) and sodium hydroxide(17.1 g of a 50% aqueous solution, 214 mmol) were added to a solution ofthe title compound of Step D (5.11 g, 21.4 mmol) in dioxane (250 mL) atroom temperature. Chlorodifluoromethane was condensed with a cold fingertrap and added to the reaction mixture until the mixture was saturated.The reaction mixture was allowed to stir at room temperature overnight.The reaction mixture was slowly poured into water. The resulting mixturewas extracted with ethyl acetate three times. The combined organicextracts were dried (MgSO₄), filtered, and concentrated under reducedpressure to give a dark-brown oil. Flash chromatography of this brownoil on silica gel, eluting with 1:25 ethyl acetate/hexane afforded thetitle compound of Step E as a light yellow solid melting at 86°-87° C.(3.23 g, 52%). ¹ H NMR (CDCl₃): δ2.57 (s,3H), 7.75 (t, 1H), 7.84 (s,1H), 7.92 (s, 1H), 8.58 (s, 1H).

Step F: Preparation of (2,2-difluoro-1,3-benzodioxol-4-yl)boronic acid

A solution of n-butyllithium (5.57 mL of a 2.5M solution in hexanes,13.9 mmol) was added to dry tetrahydrofuran (75 mL) at room temperatureunder a nitrogen atmosphere. The resulting solution was cooled to -15°C. and N,N,N',N'-tetramethylenediamine (2.10 mL, 13.9 mmol) was addeddropwise. The reaction was stirred at -15° C. for 0.5 h and then2,2-difluoro-1,3-benzodioxole was added dropwise while maintaining thereaction temperature below -10° C. After the addition was complete, thereaction was stirred at -15° C. for 1 h before a solution oftrimethylborate (1.58 mL, 13.9 mmol) in dry tetrahydrofuran (5 mL) wasadded dropwise while maintaining the reaction temperature below -10° C.The reaction mixture was stirred at -10° C. for 1 h and then allowed tocome to room temperature while stirring overnight. To the reactionmixture was added a 1N solution of hydrochloric acid and thenconcentrated hydrochloric acid until the solution was strongly acidic.The acidic solution was poured into water. The resulting mixture wassaturated with sodium chloride and extracted with diethyl ether threetimes. The combined organic extracts were dried (MgSO₄), filtered, andconcentrated under reduced pressure to give a dark-brown oil. The oilwas suspended in boiling petroleum ether and the hot solution filteredto remove a small amount of brown solid. The filtrate was then cooledand filtered to obtain a light-gray solid. The filtrate was concentratedunder reduced pressure to give a light-brown solid which was combinedwith the gray solid obtained from recrystallization to afford the titlecompound of Step F (1.28 g, 50%). ¹ H NMR (CDCl₃): δ4.92 (s,2H), 7.15(m,2H), 7.5 (d, 1H). ¹⁹ F NMR (CDCl₃): δ-50.33 (s,2F).

Step G: Preparation of8-(2.2-difluoro-1,3-benzodioxol-4-yl)-2-(difluoromethoxy)-6-methylquinoxaline

To a solution of the title compound of Step E (1.65 g, 5.73 mmol) inethylene glycol dimethyl ether (25 mL) was added the title compound ofStep F (1.73 g, 8.59 mmol), a solution of sodium carbonate (1.82 g, 17.2mmol) in water (15 mL) and bis(triphenylphosphine) palladium (II)chloride (201 mg, 0.286 mmol). The mixture was heated at refluxovernight, then cooled to room temperature and poured into water. Themixture was extracted twice with ethyl acetate. The combined organicextracts were dried (MgSO₄), filtered, and concentrated under reducedpressure to give a dark-brown oil. Flash chromatography of this oil onsilica gel eluting with 1:25 ethyl acetate/hexane afforded the titlecompound of Step G, a compound of the invention, as light-yellow solidmelting at 154°-155° C. (525 mg, 25%). ¹ H NMR (CDCl₃): δ2.64 (s,3H),7.15-7.25 (m,3H), 7.39 (t, 1H), 7.7 (s, 1H), 7.97 (s, 1H), 8.62 (s, 1H).

EXAMPLE 2

Step A: Preparation of 5-bromo-2,2-difluoro- 1,3-benzodioxole

Iron powder (2.8 g, 50 mmol) was added to a solution of2,2-difluoro-1,3-benzodioxole (15.8 g, 100 mmol) in carbon tetrachloride(200 mL) at 0° C. under a nitrogen atmosphere. Bromine (5.2 mL, 100mmol) was then added to the mixture dropwise over 15 min. The reactionwas heated to reflux for 1 h and then stirred at room temperatureovernight. The mixture was filtered through Celite and the filtrate waswashed with 0.1N sodium thiosulfate solution. The organic layer was thendried (MgSO₄), filtered, and concentrated under reduced pressure toafford the title compound of Step A as an oil (15.2 g, 64%). ¹ H NMR(CDCl₃): δ6.96 (m, 1H), 7.22 (m,2H).

Step B: Preparation of (2,2-difluoro-1,3-benzodioxol-5-yl)boronic acid

A solution of the title compound of Step A (15 g, 63 mmol) intetrahydrofuran (approximately 200 mL) was cooled to -78° C. under anitrogen atmosphere. A solution of n-butyllithium (40 mL of a 1.6Msolution in hexanes) was added dropwise while maintaining the reactiontemperature below -55° C. The reaction mixture was stirred at -78° C.for 20 min before a solution of triisopropylborate (29.4 mL, 127 mmol)in tetrahydrofuran (approximately 50 mL) was added dropwise over 30 min.The reaction was allowed to come to room temperature while stirring for5 h. The reaction mixture was then partitioned between diethyl ether and1M hydrochloric acid solution. The organic layer was separated, dried(MgSO₄), filtered, and concentrated under reduced pressure to afford thetitle compound of Step B as a brown oil (15 g) which was used withoutfurther purification.

Step C: Preparation ofN-[2-(2,2-difluoro-1,3-benzodioxol-5-yl)-4-methylphenyl]acetamide

To a mixture of 2-bromo-4-methylacetanilide (1.5 g, 6.6 mmol) and thetitle compound of Step B (2.0 g, 9.9 mmol) in ethylene glycol dimethylether (20 mL) were added a solution of sodium carbonate (2.1 g, 20 mmol)in water (20 mL) and bis(triphenylphosphine) palladium (II) chloride(230 mg, 0.33 mmol). The mixture was heated at reflux overnight, andthen additional title compound of Step B (1.0 g, 4.9 mmol) and sodiumcarbonate (1.0 g, 9.4 mmol) as a solution in water (approximately 10 mL)were added. The mixture was heated at reflux an additional 6 h and thenallowed to come to room temperature. The mixture was poured into waterand the aqueous mixture was extracted with ethyl acetate four times. Thecombined organic extracts were dried (MgSO₄), filtered and concentratedunder reduced pressure to give a dark-brown oil. The oil was purified byflash chromatography on silica gel, eluting with 1:4 ethylacetate/hexane to afford the title compound of Step C, a compound of theinvention, as a light brown solid melting at 105°-107° C. (205 mg, 10%).¹ H NMR (CD₃ COCD₃): δ1.95 (s,3H), 2.36 (s,3H), 7.2(m,2H), 7.25(m,3H),7.8(m, 1H), 8.55(br s, 1H).

EXAMPLE 3

Step A: Preparationof2-(2,2-difluoro-1,3-benzodioxol-4-yl)-4-methylbenzenamine

To a solution of N-[2-(2,2-difluoro- 1,3-benzodioxol-4-yl)-4-methylphenyl]acetamide (600 mg, 1.97 mmol, preparedaccording to the procedure for the title compound of Step C of Example2) in ethanol (10 mL) was added a solution of sodium hydroxide (0.6 mLof a 50% aqueous solution). The resulting mixture was heated to refluxfor 3 h and then allowed to stir at room temperature overnight. After anadditional 8.5 h at reflux during which time a second portion of sodiumhydroxide solution (0.6 mL of a 50% aqueous solution) was added, thereaction was again allowed to stir at room temperature overnight. Afteranother 8 h at reflux, the reaction mixture was cooled to roomtemperature and the solvent was removed under reduced pressure. Theresulting residue was partitioned between water and ethyl acetate, theorganic layer was separated, and the aqueous phase was extracted threetimes with ethyl acetate. The combined organic layers were dried(MgSO₄), filtered, and concentrated under reduced pressure to afford thetitle compound of Step A as a brown liquid (505 mg, 98%). ¹ H NMR(CDCl₃): δ2.29 (s,3H), 6.75 (d, 1H), 7.05 (m,3H), 7.15 (m,2H).

Step B: Preparation ofN-[2-(2,2-difluoro-1,3-benzodioxol-4-yl)-4-methylphenyl]cyclopropanecarboxamide

A solution of the title compound of Step A (500 mg, 1.90 mmol) in drytetrahydrofuran (10 mL) was cooled in an ice water bath. Triethylamine(592 μL, 3.80 mmol) was added followed by slow addition ofcyclopropanecarbonyl chloride (172 μL, 1.90 mmol). The reaction wasallowed to come to room temperature while stirring overnight. Thereaction mixture was poured into water. The aqueous mixture wassaturated with sodium chloride and extracted with ethyl acetate twice.The organic extracts were dried (MgSO₄), filtered, and concentratedunder reduced pressure to give a beige solid. Flash chromatography ofthe crude product on silica gel eluting with 1:9 ethyl acetate/hexaneafforded the title compound of Step B, a compound of the invention, as awhite solid melting at 138°-139° C. (565 mg, 90%). ¹ H NMR (CDCl₃):δ0.75 (m,2H), 1.0 (m,2H), 1.3 (m, 1H), 2.37 (s,3H), 7.1 (m,3H), 7.2-7.25(m,3H), 7.9 (d, 1H).

EXAMPLE 4

Step A: Preparation ofN-(2-borono-4-methylphenyl)-2,2-dimethylpropanamide

To a solution of N-(4-methylphenyl)-2,2-dimethylpropanamide (80.0 g, 418mmol) in 1000 mL of dry tetrahydrofuran (THF) cooled to -78° C. under anitrogen atmosphere was added a solution of n-butyllithium (502 mL, 1250mmol of a 2.5M solution in hexanes) over 1 h while maintaining thetemperature below -60° C. The reaction mixture was allowed to warm toroom temperature overnight.

The reaction mixture was cooled to -5° C. and trimethyl borate (200 mL)was added dropwise over 1 h while maintaining the temperature below 0°C. Stirring was continued while the reaction was allowed to warm to roomtemperature over 3 h. First, 100 mL of water was added, and thenconcentrated hydrochloric acid was added dropwise to form a stronglyacidic solution. The organic solvents were removed under reducedpressure and then 300 mL of water and 500 mL of diethyl ether were addedto form a slurry. The mixture was stirred until a fine, whiteprecipitate developed which was collected by filtration. The solids werewashed five times with 200 mL portions of diethyl ether and then twicewith 200 mL portions of hexane. The white solid was then suspended in250 mL of acetone with stirring and 1000 mL of water was added over 40min. The resulting white precipitate was collected by filtration, washedwith water, then with diethyl ether and hexane, and dried in a vacuumoven to afford the title compound of Step A as a white solidmelting >270° C. (38.37 g). ¹ H NMR (CDCl₃): δ1.07 (s,9H), 2.37 (s,3H),7.2 (d, 1H), 7.81 (s, 1H), 7.95 (d, 1H), 10.08 (br s,1H).

Step B: Preparation of 4-bromo-2,2-difluoro-1,3-benzodioxole

A solution of2,2-difluoro-1,3-benzodioxole (2.00 g, 12.6 mmol) in drytetrahydrofuran (75 mL) was cooled to -78° C. under a nitrogenatmosphere. A solution of n-butyllithium (5.57 mL, 13.9 mmol of a 2.5Msolution in hexanes) was added dropwise while maintaining thetemperature below -65° C. The reaction mixture was stirred at -78° C.for an additional 30 min after the addition was complete, and then1,2-dibromotetrafluoroethane (1.66 mL, 13.9 mmol) was added dropwise.After the addition was complete, the reaction mixture was allowed tocome to room temperature. After adding a small amount of water to thereaction slowly, the reaction mixture was poured into water and theaqueous mixture was saturated with sodium chloride. This mixture wasextracted with diethyl ether. The organic extracts were dried (MgSO₄),filtered, and concentrated under reduced pressure to afford the titlecompound of Step B as a light yellow liquid (2.7 g, 90%). ¹ H NMR(CDCl₃): δ7.0 (m, 1H), 7.2 (m,2H). ¹⁹ F NMR (CDCl₃): δ-49.99 (s,2F).

Step C: Preparation ofN-[2-(2,2-difluoro-1,3-benzodioxol-4-yl)-4-methylphenyl]-2,2-dimethylpropanamide

To a mixture of the title compound of Step B (10.0 g, 42.2 mmol) and thetitle compound of Step A (4.96 g, 21.1 mmol) in ethylene glycol dimethylether (100 mL) were added a solution of sodium carbonate (4.47 g, 42.2mmol) in water (25 mL) and bis(triphenylphosphine) palladium (II)chloride (740 mg, 1.05 mmol) at room temperature. The mixture was heatedat reflux for 2 h and then allowed to come to room temperature. Thesolvent was removed under reduced pressure and the residue was suspendedin water. The aqueous mixture was extracted with ethyl acetate threetimes. The organic extracts were dried (MgSO₄), filtered, andconcentrated under reduced pressure to obtain a brown liquid. Flashchromatography of the crude product on silica gel eluting with 1:6 ethylacetate/hexane afforded the title compound of Step C, a compound of theinvention, as a yellow oily solid (8 g, 55%). ¹ H NMR (CDCl₃): δ1.12(s,9H), 2.37 (s,3H), 7.1 (m,2H), 7.12 (s, 1H), 7.2 (t, 1H), 7.25 (m,1H),7.3 (br s,1H), 7.9 (d, 1H).

EXAMPLE 5

Step A: Preparation of 5-bromo-2,2,3,3-tetrafluoro-2,3-dihydro-1,4-benzodioxin

A solution of 2,2,3,3-tetrafluoro-2,3-dihydro-1,4-benzodioxin (5.00 g,24.0 mmol) in dry tetrahydrofuran (150 mL) is cooled to -78° C. under anitrogen atmosphere. A solution of n-butyllithium (10.6 mL, 26.4 mmol ofa 2.5M solution in hexanes) is added dropwise while maintaining thereaction temperature below -65° C. The reaction mixture is stirred at-78° C. for 30 min and then 1,2-dibromotetrafluoroethane (3.16 mL, 26.4mmol) is added dropwise. After this addition is complete, the reactionmixture is allowed to come to room temperature. A small mount of wateris slowly added to the mixture which is then poured into water. Theaqueous mixture is saturated with sodium chloride and is extracted withdiethyl ether. The combined organic extracts are dried (MgSO₄),filtered, and concentrated under reduced pressure to afford the titlecompound of Step A.

Step B: Preparation ofN-[2-(2,2,3,3-tetrafluoro-2,3-dihydro-1,4-benzodioxin-5-yl)-4-methylphenyl]-2,2-dimethylpropanamide

The title compound of Step A of this example (6.00 g, 20.9 mmol), thetitle compound of Step A in Example 4 (4.91 g, 20.9 mmol),bis(triphenylphospine) palladium (II) chloride (734 mg, 1.05 mmol) and asolution of sodium carbonate (4.43 g, 41.8 mmol) in water (25 mL) arecombined in ethylene glycol dimethyl ether (100 mL) at room temperature.The mixture is heated to reflux overnight. The reaction mixture iscooled to room temperature and is poured into water. This mixture isextracted with ethyl acetate. The organic extracts are dried (MgSO₄),filtered, and concentrated under reduced pressure. Flash chromatographyof the crude reaction product on silica gel affords the title compoundof Step B, a compound of the invention.

By the procedures described herein, the following compounds of Tables 1to 14 can be prepared. The following abbreviations are used in theTables which follow: n=normal, Me=methyl, Et=ethyl, nPr=n-propyl,nBu=n-butyl, Ph=phenyl, CN=cyano, and NO₂ =nitro.

                                      TABLE 1                                     __________________________________________________________________________     ##STR19##                                                                    X   R.sup.3 R.sup.4                                                                          R.sup.5                                                                             X   R.sup.3                                                                             R.sup.4                                                                          R.sup.5                                     __________________________________________________________________________    R.sup.7 = H                                                                   CH  Me      H  CF.sub.3                                                                            CH  Me    F  CF.sub.3                                    CH  Et      H  CF.sub.3                                                                            CH  Me    F  OCHF.sub.2                                  CH  nPr     H  CF.sub.3                                                                            N   Me    H  CF.sub.3                                    CH  MeO     H  CF.sub.3                                                                            N   Et    H  CF.sub.3                                    CH  EtO     H  CF.sub.3                                                                            N   Me    H  OCHF.sub.2                                  CH  MeS     H  CF.sub.3                                                                            N   Et    H  OCHF.sub.2                                  CH  EtS     H  CF.sub.3                                                                            CH  Me    H  OCH.sub.2 CF.sub.3                          CH  MeNH    H  CF.sub.3                                                                            CH  Me    H  CN                                          CH  Me.sub.2 N                                                                            H  CF.sub.3                                                                            CH  Me    H  CH.sub.3                                    CH  MeOCH.sub.2                                                                           H  CF.sub.3                                                                            CH  Me    H  Cl                                          CH  MeCHCH  H  CF.sub.3                                                                            CH  Me    H  SCF.sub.3                                   CH  HCC     H  CF.sub.3                                                                            CH  Me    H  OMe                                         CH  Me      H  OCHF.sub.2                                                                          CH  Me    H  SMe                                         CH  Et      H  OCHF.sub.2                                                                          CH  Me    H  OEt                                         CH  nPr     H  OCHF.sub.2                                                                          CH  Me    H  OCF.sub.2 CHF.sub.2                         CH  MeO     H  OCHF.sub.2                                                                          CH  Me    H  CHCHCF.sub.3                                CH  EtO     H  OCHF.sub.2                                                                          CH  Me    H  SCHF.sub.2                                  CH  MeS     H  OCHF.sub.2                                                                          CH  Me    H  SO.sub.2 CHF.sub.2                          CH  EtS     H  OCHF.sub.2                                                                          CH  Et    H  SCHF.sub.2                                  CH  MeNH    H  OCHF.sub.2                                                                          N   Me    H  CF.sub.3                                    CH  Me.sub.2 N                                                                            H  OCHF.sub.2                                                                          N   Me    H  OCHF.sub.2                                  CH  MeOCH.sub.2                                                                           H  OCHF.sub.2                                                                          N   Me    F  CF.sub.3                                    CH  MeCHCH  H  OCHF.sub.2                                                                          N   Me    F  OCHF.sub.2                                  CH  HCC     H  OCHF.sub.2                                                                          N   Me    H  OMe                                         N   Et      H  CF.sub.3                                                                            CH  nPr   H  SCF.sub.3                                   N   Et      H  OCHF.sub.2                                                                          CH  MeOCH.sub.2                                                                         H  SCHF.sub.2                                  CH  CH.sub.3                                                                              H  OCHMe.sub.2                                                                         CH  HCC   H  SCF.sub.3                                   R.sup.5 = H                                                                   CH  Me      H  CF.sub.3                                                                            CH  Me    F  CF.sub.3                                    CH  Et      H  CF.sub.3                                                                            CH  Me    F  OCHF.sub.2                                  CH  nPr     H  CF.sub.3                                                                            N   Me    H  CF.sub.3                                    CH  MeO     H  CF.sub.3                                                                            N   Et    H  CF.sub.3                                    CH  EtO     H  CF.sub.3                                                                            N   Me    H  OCHF.sub.2                                  CH  MeS     H  CF.sub.3                                                                            N   Et    H  OCHF.sub.2                                  CH  EtS     H  CF.sub.3                                                                            CH  Me    H  OCH.sub.2 CF.sub.3                          CH  MeNH    H  CF.sub.3                                                                            CH  Me    H  CN                                          CH  Me.sub.2 N                                                                            H  CF.sub.3                                                                            CH  Me    H  CH.sub.3                                    CH  MeOCH.sub.2                                                                           H  CF.sub.3                                                                            CH  Me    H  Cl                                          CH  MeCHCH  H  CF.sub.3                                                                            CH  Me    H  SCF.sub.3                                   CH  HCC     H  CF.sub.3                                                                            CH  Me    H  OMe                                         CH  Me      H  OCHF.sub.2                                                                          CH  Me    H  SMe                                         CH  Et      H  OCHF.sub.2                                                                          CH  Me    H  OEt                                         CH  nPr     H  OCHF.sub.2                                                                          CH  Me    H  OCF.sub.2 CHF.sub.2                         CH  MeO     H  OCHF.sub.2                                                                          CH  Me    H  CHCHCF.sub.3                                CH  EtO     H  OCHF.sub.2                                                                          CH  Me    H  SCHF.sub.2                                  CH  MeS     H  OCHF.sub.2                                                                          CH  Me    H  SO.sub.2 CHF.sub.2                          CH  EtS     H  OCHF.sub.2                                                                          CH  Et    H  SCHF.sub.2                                  CH  MeNH    H  OCHF.sub.2                                                                          N   Me    H  CF.sub.3                                    CH  Me.sub.2 N                                                                            H  OCHF.sub.2                                                                          N   Me    H  OCHF.sub.2                                  CH  MeOCH.sub.2                                                                           H  OCHF.sub.2                                                                          N   Me    F  CF.sub.3                                    CH  MeCHCH  H  OCHF.sub.2                                                                          N   Me    F  OCHF.sub.2                                  CH  HCC     H  OCHF.sub.2                                                                          N   Me    H  OMe                                         N   Et      H  CF.sub.3                                                                            CH  nPr   H  SCF.sub.3                                   N   Et      H  OCHF.sub.2                                                                          CH  MeOCH.sub.2                                                                         H  SCHF.sub.2                                  CH  CH.sub.3                                                                              H  OCHMe.sub.2                                                                         CH  HCC   H  SCF.sub.3                                   __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR20##                                                                    X   R.sup.3 R.sup.4                                                                          R.sup.5                                                                             X   R.sup.3                                                                             R.sup.4                                                                          R.sup.5                                     __________________________________________________________________________    R.sup.7 = H                                                                   CH  Me      H  CF.sub.3                                                                            CH  Me    F  CF.sub.3                                    CH  Et      H  CF.sub.3                                                                            CH  Me    F  OCHF.sub.2                                  CH  nPr     H  CF.sub.3                                                                            N   Me    H  CF.sub.3                                    CH  MeO     H  CF.sub.3                                                                            N   Et    H  CF.sub.3                                    CH  EtO     H  CF.sub.3                                                                            N   Me    H  OCHF.sub.2                                  CH  MeS     H  CF.sub.3                                                                            N   Et    H  OCHF.sub.2                                  CH  EtS     H  CF.sub.3                                                                            CH  Me    H  OCH.sub.2 CF.sub.3                          CH  MeNH    H  CF.sub.3                                                                            CH  Me    H  CN                                          CH  Me.sub.2 N                                                                            H  CF.sub.3                                                                            CH  Me    H  CH.sub.3                                    CH  MeOCH.sub.2                                                                           H  CF.sub.3                                                                            CH  Me    H  Cl                                          CH  MeCHCH  H  CF.sub.3                                                                            CH  Me    H  SCF.sub.3                                   CH  HCC     H  CF.sub.3                                                                            CH  Me    H  OMe                                         CH  Me      H  OCHF.sub.2                                                                          CH  Me    H  SMe                                         CH  Et      H  OCHF.sub.2                                                                          CH  Me    H  OEt                                         CH  nPr     H  OCHF.sub.2                                                                          CH  Me    H  OCF.sub.2 CHF.sub.2                         CH  MeO     H  OCHF.sub.2                                                                          CH  Me    H  CHCHCF.sub.3                                CH  EtO     H  OCHF.sub.2                                                                          CH  Me    H  SCHF.sub.2                                  CH  MeS     H  OCHF.sub.2                                                                          CH  Me    H  SO.sub.2 CHF.sub.2                          CH  EtS     H  OCHF.sub.2                                                                          CH  Et    H  SCHF.sub.2                                  CH  MeNH    H  OCHF.sub.2                                                                          N   Me    H  CF.sub.3                                    CH  Me.sub.2 N                                                                            H  OCHF.sub.2                                                                          N   Me    H  OCHF.sub.2                                  CH  MeOCH.sub.2                                                                           H  OCHF.sub.2                                                                          N   Me    F  CF.sub.3                                    CH  MeCHCH  H  OCHF.sub.2                                                                          N   Me    F  OCHF.sub.2                                  CH  HCC     H  OCHF.sub.2                                                                          N   Me    H  OMe                                         N   Et      H  CF.sub.3                                                                            CH  nPr   H  SCF.sub.3                                   N   Et      H  OCHF.sub.2                                                                          CH  MeOCH.sub.2                                                                         H  SCHF.sub.2                                  CH  CH.sub.3                                                                              H  OCHMe.sub.2                                                                         CH  HCC   H  SCF.sub.3                                   R.sup.5 = H                                                                   CH  Me      H  CF.sub.3                                                                            CH  Me    F  CF.sub.3                                    CH  Et      H  CF.sub.3                                                                            CH  Me    F  OCHF.sub.2                                  CH  nPr     H  CF.sub.3                                                                            N   Me    H  CF.sub.3                                    CH  MeO     H  CF.sub.3                                                                            N   Et    H  CF.sub.3                                    CH  EtO     H  CF.sub.3                                                                            N   Me    H  OCHF.sub.2                                  CH  MeS     H  CF.sub.3                                                                            N   Et    H  OCHF.sub.2                                  CH  EtS     H  CF.sub.3                                                                            CH  Me    H  OCH.sub.2 CF.sub.3                          CH  MeNH    H  CF.sub.3                                                                            CH  Me    H  CN                                          CH  Me.sub.2 N                                                                            H  CF.sub.3                                                                            CH  Me    H  CH.sub.3                                    CH  MeOCH.sub.2                                                                           H  CF.sub.3                                                                            CH  Me    H  Cl                                          CH  MeCHCH  H  CF.sub.3                                                                            CH  Me    H  SCF.sub.3                                   CH  HCC     H  CF.sub.3                                                                            CH  Me    H  OMe                                         CH  Me      H  OCHF.sub.2                                                                          CH  Me    H  SMe                                         CH  Et      H  OCHF.sub.2                                                                          CH  Me    H  OEt                                         CH  nPr     H  OCHF.sub.2                                                                          CH  Me    H  OCF.sub.2 CHF.sub.2                         CH  MeO     H  OCHF.sub.2                                                                          CH  Me    H  CHCHCF.sub.3                                CH  EtO     H  OCHF.sub.2                                                                          CH  Me    H  SCHF.sub.2                                  CH  MeS     H  OCHF.sub.2                                                                          CH  Me    H  SO.sub.2 CHF.sub.2                          CH  EtS     H  OCHF.sub.2                                                                          CH  Et    H  SCHF.sub.2                                  CH  MeNH    H  OCHF.sub.2                                                                          N   Me    H  CF.sub.3                                    CH  Me.sub.2 N                                                                            H  OCHF.sub.2                                                                          N   Me    H  OCHF.sub.2                                  CH  MeOCH.sub.2                                                                           H  OCHF.sub.2                                                                          N   Me    F  CF.sub.3                                    CH  MeCHCH  H  OCHF.sub.2                                                                          N   Me    F  OCHF.sub.2                                  CH  HCC     H  OCHF.sub.2                                                                          N   Me    H  OMe                                         N   Et      H  CF.sub.3                                                                            CH  nPr   H  SCF.sub.3                                   N   Et      H  OCHF.sub.2                                                                          CH  MeOCH.sub.2                                                                         H  SCHF.sub.2                                  CH  CH.sub.3                                                                              H  OCHMe.sub.2                                                                         CH  HCC   H  SCF.sub.3                                   __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________     ##STR21##                                                                    X   R.sup.3 R.sup.4                                                                          R.sup.5                                                                             X   R.sup.3                                                                             R.sup.4                                                                          R.sup.5                                     __________________________________________________________________________    Y = N                                                                         CH  Me      H  CF.sub.3                                                                            CH  HCC   H  OCHF.sub.2                                  CH  Et      H  CF.sub.3                                                                            CH  Me    F  CF.sub.3                                    CH  nPr     H  CF.sub.3                                                                            CH  Me    F  OCHF.sub.2                                  CH  MeO     H  CF.sub.3                                                                            N   Me    H  CF.sub.3                                    CH  EtO     H  CF.sub.3                                                                            N   Me    H  OCHF.sub.2                                  CH  MeS     H  CF.sub.3                                                                            N   Me    H  SCHF.sub.2                                  CH  EtS     H  CF.sub.3                                                                            N   Me    H  SCF.sub.3                                   CH  MeNH    H  CF.sub.3                                                                            N   Et    H  OCHF.sub.2                                  CH  Me.sub.2 N                                                                            H  CF.sub.3                                                                            CH  Me    H  OCH.sub.2 CF.sub.3                          CH  MeOCH.sub.2                                                                           H  CF.sub.3                                                                            CH  Me    H  CN                                          CH  MeCHCH  H  CF.sub.3                                                                            CH  Me    H  CH.sub.3                                    CH  HCC     H  CF.sub.3                                                                            CH  Me    H  Cl                                          CH  Me      H  OCHF.sub.2                                                                          CH  Me    H  OMe                                         CH  Et      H  OCHF.sub.2                                                                          CH  Me    H  SMe                                         CH  nPr     H  OCHF.sub.2                                                                          CH  Me    H  OEt                                         CH  MeO     H  OCHF.sub.2                                                                          CH  Me    H  OCF.sub.2 CHF.sub.2                         CH  EtO     H  OCHF.sub.2                                                                          CH  Me    H  CHCHCF.sub.3                                CH  MeS     H  OCHF.sub.2                                                                          CH  Me    H  SO.sub.2 CHF.sub.2                          CH  EtS     H  OCHF.sub.2                                                                          CH  Me    H  OCHMe.sub.2                                 CH  MeNH    H  OCHF.sub.2                                                                          CH  Et    H  SCF.sub.3                                   CH  Me.sub.2 N                                                                            H  OCHF.sub.2                                                                          CH  nPr   H  SCHF.sub.2                                  CH  MeOCH.sub.2                                                                           H  OCHF.sub.2                                                                          CH  MeOCH.sub.2                                                                         H  SCF.sub.3                                   CH  MeCHCH  H  OCHF.sub.2                                                                          CH  HCC   H  SCHF.sub.2                                  Y = CH                                                                        CH  Me      H  CF.sub.3                                                                            CH  HCC   H  OCHF.sub.2                                  CH  Et      H  CF.sub.3                                                                            CH  Me    F  CF.sub.3                                    CH  nPr     H  CF.sub.3                                                                            CH  Me    F  OCHF.sub.2                                  CH  MeO     H  CF.sub.3                                                                            N   Me    H  CF.sub.3                                    CH  EtO     H  CF.sub.3                                                                            N   Me    H  OCHF.sub.2                                  CH  MeS     H  CF.sub.3                                                                            N   Me    H  SCHF.sub.2                                  CH  EtS     H  CF.sub.3                                                                            N   Me    H  SCF.sub.3                                   CH  MeNH    H  CF.sub.3                                                                            N   Et    H  OCHF.sub.2                                  CH  Me.sub.2 N                                                                            H  CF.sub.3                                                                            CH  Me    H  OCH.sub.2 CF.sub.3                          CH  MeOCH.sub.2                                                                           H  CF.sub.3                                                                            CH  Me    H  CN                                          CH  CH.sub.2CH                                                                            H  CF.sub.3                                                                            CH  Me    H  CH.sub.3                                    CH  HCC     H  CF.sub.3                                                                            CH  Me    H  Cl                                          CH  Me      H  OCHF.sub.2                                                                          CH  Me    H  OMe                                         CH  Et      H  OCHF.sub.2                                                                          CH  Me    H  SMe                                         CH  nPr     H  OCHF.sub.2                                                                          CH  Me    H  OEt                                         CH  MeO     H  OCHF.sub.2                                                                          CH  Me    H  OCF.sub.2 CHF.sub.2                         CH  EtO     H  OCHF.sub.2                                                                          CH  Me    H  CHCHCF.sub.3                                CH  MeS     H  OCHF.sub.2                                                                          CH  Me    H  SO.sub.2 CHF.sub.2                          CH  EtS     H  OCHF.sub.2                                                                          CH  Me    H  OCHMe.sub.2                                 CH  MeNH    H  OCHF.sub.2                                                                          CH  Et    H  SCF.sub.3                                   CH  Me.sub.2 N                                                                            H  OCHF.sub.2                                                                          CH  nPr   H  SCHF.sub.2                                  CH  MeOCH.sub.2                                                                           H  OCHF.sub.2                                                                          CH  MeOCH.sub.2                                                                         H  SCF.sub.3                                   CH  CH.sub.2CH                                                                            H  OCHF.sub.2                                                                          CH  HCC   H  SCHF.sub.2                                  __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________     ##STR22##                                                                    X   R.sup.3 R.sup.4                                                                          R.sup.5                                                                             X   R.sup.3                                                                             R.sup.4                                                                          R.sup.5                                     __________________________________________________________________________    Y = N                                                                         CH  Me      H  CF.sub.3                                                                            CH  HCC   H  OCHF.sub.2                                  CH  Et      H  CF.sub.3                                                                            CH  Me    F  CF.sub.3                                    CH  nPr     H  CF.sub.3                                                                            CH  Me    F  OCHF.sub.2                                  CH  MeO     H  CF.sub.3                                                                            N   Me    H  CF.sub.3                                    CH  EtO     H  CF.sub.3                                                                            N   Me    H  OCHF.sub.2                                  CH  MeS     H  CF.sub.3                                                                            N   Me    H  SCHF.sub.2                                  CH  EtS     H  CF.sub.3                                                                            N   Me    H  SCF.sub.3                                   CH  MeNH    H  CF.sub.3                                                                            N   Et    H  OCHF.sub.2                                  CH  Me.sub.2 N                                                                            H  CF.sub.3                                                                            CH  Me    H  OCH.sub.2 CF.sub.3                          CH  MeOCH.sub.2                                                                           H  CF.sub.3                                                                            CH  Me    H  CN                                          CH  MeCHCH  H  CF.sub.3                                                                            CH  Me    H  CH.sub.3                                    CH  HCC     H  CF.sub.3                                                                            CH  Me    H  Cl                                          CH  Me      H  OCHF.sub.2                                                                          CH  Me    H  OMe                                         CH  Et      H  OCHF.sub.2                                                                          CH  Me    H  SMe                                         CH  nPr     H  OCHF.sub.2                                                                          CH  Me    H  OEt                                         CH  MeO     H  OCHF.sub.2                                                                          CH  Me    H  OCF.sub.2 CHF.sub.2                         CH  EtO     H  OCHF.sub.2                                                                          CH  Me    H  CHCHCF.sub.3                                CH  MeS     H  OCHF.sub.2                                                                          CH  Me    H  SO.sub.2 CHF.sub.2                          CH  EtS     H  OCHF.sub.2                                                                          CH  Me    H  OCHMe.sub.2                                 CH  MeNH    H  OCHF.sub.2                                                                          CH  Et    H  SCF.sub.3                                   CH  Me.sub.2 N                                                                            H  OCHF.sub.2                                                                          CH  nPr   H  SCHF.sub.2                                  CH  MeOCH.sub.2                                                                           H  OCHF.sub.2                                                                          CH  MeOCH.sub.2                                                                         H  SCF.sub.3                                   CH  MeCHCH  H  OCHF.sub.2                                                                          CH  HCC   H  SCHF.sub.2                                  Y = CH                                                                        CH  Me      H  CF.sub.3                                                                            CH  HCC   H  OCHF.sub.2                                  CH  Et      H  CF.sub.3                                                                            CH  Me    F  CF.sub.3                                    CH  nPr     H  CF.sub.3                                                                            CH  Me    F  OCHF.sub.2                                  CH  MeO     H  CF.sub.3                                                                            N   Me    H  CF.sub.3                                    CH  EtO     H  CF.sub.3                                                                            N   Me    H  OCHF.sub.2                                  CH  MeS     H  CF.sub.3                                                                            N   Me    H  SCHF.sub.2                                  CH  EtS     H  CF.sub.3                                                                            N   Me    H  SCF.sub.3                                   CH  MeNH    H  CF.sub.3                                                                            N   Et    H  OCHF.sub.2                                  CH  Me.sub.2 N                                                                            H  CF.sub.3                                                                            CH  Me    H  OCH.sub.2 CF.sub.3                          CH  MeOCH.sub.2                                                                           H  CF.sub.3                                                                            CH  Me    H  CN                                          CH  MeCHCH  H  CF.sub.3                                                                            CH  Me    H  CH.sub.3                                    CH  HCC     H  CF.sub.3                                                                            CH  Me    H  Cl                                          CH  Me      H  OCHF.sub.2                                                                          CH  Me    H  OMe                                         CH  Et      H  OCHF.sub.2                                                                          CH  Me    H  SMe                                         CH  nPr     H  OCHF.sub.2                                                                          CH  Me    H  OEt                                         CH  MeO     H  OCHF.sub.2                                                                          CH  Me    H  OCF.sub.2 CHF.sub.2                         CH  EtO     H  OCHF.sub.2                                                                          CH  Me    H  CHCHCF.sub.3                                CH  MeS     H  OCHF.sub.2                                                                          CH  Me    H  SO.sub.2 CHF.sub.2                          CH  EtS     H  OCHF.sub.2                                                                          CH  Me    H  OCHMe.sub.2                                 CH  MeNH    H  OCHF.sub.2                                                                          CH  Et    H  SCF.sub.3                                   CH  Me.sub.2 N                                                                            H  OCHF.sub.2                                                                          CH  nPr   H  SCHF.sub.2                                  CH  MeOCH.sub.2                                                                           H  OCHF.sub.2                                                                          CH  MeOCH.sub.2                                                                         H  SCF.sub.3                                   CH  CH.sub.2CH                                                                            H  OCHF.sub.2                                                                          CH  HCC   H  SCHF.sub.2                                  __________________________________________________________________________

                  TABLE 5                                                         ______________________________________                                         ##STR23##                                                                    X       Y        Z       R.sup.3                                                                              R.sup.4                                                                            R.sup.5                                  ______________________________________                                        CH      N        CH      Me     H    CF.sub.3                                 CH      N        CH      Me     H    OCHF.sub.2                               CH      N        CH      Me     H    SCF.sub.3                                CH      N        CH      Me     H    SCHF.sub.2                               CH      N        CH      Me     H    OCH.sub.2 CF.sub.3                       CH      CH       N       Me     H    CF.sub.3                                 CH      CH       N       Me     H    OCHF.sub.2                               CH      CH       N       Me     H    SCF.sub.3                                CH      CH       N       Me     H    SCHF.sub.2                               CH      CH       N       Me     H    OCH.sub.2 CF.sub.3                       N       N        CH      Me     H    CF.sub.3                                 N       N        CH      Me     H    OCHF.sub.2                               N       CH       N       Me     H    CF.sub.3                                 N       CH       N       Me     H    OCHF.sub.2                               CH      N        CH      Me     F    OCHF.sub.2                               CH      CH       N       Me     F    CF.sub.3                                 CH      N        CH      Et     H    CF.sub.3                                 CH      CH       N       Et     H    OCHF.sub.2                               CH      N        CH      nPr    H    OCHF.sub.2                               ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                         ##STR24##                                                                    X       Y        Z       R.sup.3                                                                              R.sup.4                                                                            R.sup.5                                  ______________________________________                                        CH      N        CH      Me     H    CF.sub.3                                 CH      N        CH      Me     H    OCHF.sub.2                               CH      N        CH      Me     H    SCF.sub.3                                CH      N        CH      Me     H    SCHF.sub.2                               CH      N        CH      Me     H    OCH.sub.2 CF.sub.3                       CH      CH       N       Me     H    CF.sub.3                                 CH      CH       N       Me     H    OCHF.sub.2                               CH      CH       N       Me     H    SCF.sub.3                                CH      CH       N       Me     H    SCHF.sub.2                               CH      CH       N       Me     H    OCH.sub.2 CF.sub.3                       N       N        CH      Me     H    CF.sub.3                                 N       N        CH      Me     H    OCHF.sub.2                               N       CH       N       Me     H    CF.sub.3                                 N       CH       N       Me     H    OCHF.sub.2                               CH      N        CH      Me     F    OCHF.sub.2                               CH      CH       N       Me     F    CF.sub.3                                 CH      N        CH      Et     H    CF.sub.3                                 CH      CH       N       Et     H    OCHF.sub.2                               CH      N        CH      nPr    H    OCHF.sub.2                               ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                         ##STR25##                                                                    X           R.sup.3   R.sup.4   R.sup.7                                       ______________________________________                                        CH          Me        H         CF.sub.3                                      CH          Me        H         OCHF.sub.2                                    CH          Me        H         SCHF.sub.2                                    CH          Me        F         CF.sub.3                                      CH          Me        F         OCHF.sub.2                                    CH          Et        H         CF.sub.3                                      CH          nPr       H         OCHF.sub.2                                    N           Me        H         CF.sub.3                                      N           Me        H         OCHF.sub.2                                    N           Et        H         OCHF.sub.2                                    ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                         ##STR26##                                                                    X           R.sup.3    R.sup.4  R.sup.7                                       ______________________________________                                        CH          Me         H        CF.sub.3                                      CH          Me         H        OCHF.sub.2                                    CH          Me         H        SCHF.sub.2                                    CH          Me         F        CF.sub.3                                      CH          Me         F        OCHF.sub.2                                    CH          Et         H        CF.sub.3                                      CH          nPr        H        OCHF.sub.2                                    N           Me         H        CF.sub.3                                      N           Me         H        OCHF.sub.2                                    N           Et         H        OCHF.sub.2                                    ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                         ##STR27##                                                                    ______________________________________                                        T = O, W is a single bond, R.sup.2 = Me                                       R.sup.1            R.sup.1                                                    ______________________________________                                        Me                 CH(Me)CH.sub.2 Cl                                          CH.sub.2 F         C(Me)CHBr                                                  CH.sub.2 Cl        CHCHMe                                                     CH.sub.2 Br        CH(Me)SMe                                                  CHF.sub.2          CH(Me)OMe                                                  CHCl.sub.2         (CH.sub.2).sub.3 Me                                        CF.sub.3           CH(Me)CH.sub.2 Me                                          Et                 CH.sub.2 CHMe.sub.2                                        CH.sub.2 CF.sub.3  CMe.sub.3                                                  CH.sub.2 CH.sub.2 F                                                                              cyclobutyl                                                 CH.sub.2 CH.sub.2 Cl                                                                             1-Me-cyclopropyl                                           CH.sub.2 CH.sub.2 Br                                                                             2-Me-cyclopropyl                                           CHFMe              CH.sub.2 -cyclopropyl                                      CHClMe             CH.sub.2 C(Me)CH.sub.2                                     CHBrMe             CHCMe.sub.2                                                CH.sub.2 CHF.sub.2 CHBrCHMe.sub.2                                             CCl.sub.2 Me       CHC(CH.sub.2 Cl).sub.2                                     CH.sub.2 OMe       C(Me).sub.2 CH.sub.2 Cl                                    CH.sub.2 SMe       C(Me).sub.2 OMe                                            CH.sub.2 CF.sub.3  C(Me).sub.2 SMe                                            (CH.sub.2).sub.2 Me                                                                              (CH.sub.2).sub.4 Me                                        CHMe.sub.2         CH(CH.sub.2 CH.sub.3).sub.2                                cyclopropyl        Ph                                                         C(Me)CH.sub.2      CMe.sub.2 Br                                               ______________________________________                                        T = O, R.sup.2 = Me                                                           W          R.sup.1     W          R.sup.1                                     ______________________________________                                        O          Me          S          CH.sub.2 CHMe.sub.2                         O          Et          NH         Me                                          O          nPr         NH         Et                                          O          nBu         NH         nPr                                         O          CHMe.sub.2  NH         nBu                                         O          CH.sub.2 CHCH.sub.2                                                                       NH         CHMe.sub.2                                  O          CH.sub.2 CHMe.sub.2                                                                       NH         CH.sub.2 CHMe.sub.2                         S          Me          NMe        Me                                          S          Et          NMe        Et                                          S          nPr         NMe        nPr                                         S          CHMe.sub.2  NOMe       Me                                          ______________________________________                                        T = S, W is a single bond                                                     R.sup.1    R.sup.2     R.sup.1    R.sup.2                                     ______________________________________                                        Me         Me          CHMe.sub.2 Cl                                          Et         Me          CH.sub.2 CHMe.sub.2                                                                      Br                                          nPr        Me          cyclopropyl                                                                              Et                                          CF.sub.3   Me          CHMe.sub.2 OMe                                         CHMe.sub.2 Me          CH.sub.2 CHMe.sub.2                                                                      OEt                                         CH.sub.2 CHMe.sub.2                                                                      Me          CHMe.sub.2 CN                                          CMe.sub.3  Me          CMe.sub.3  NO.sub.2                                    cyclopropyl                                                                              Me          CMe.sub.3  NHMe                                        cyclobutyl Me          CMe.sub.3  NMe.sub.2                                   Ph         Me          cyclopropyl                                                                              Br                                          CH.sub.2 CF.sub.3                                                                        Me          CMe.sub.3  Et                                          CHCMe.sub.2                                                                              Me          CH.sub.2 CHMe.sub.2                                                                      CN                                          1-Me-cyclopropyl                                                                         Me          CHMe.sub.2 NEt.sub.2                                   CHMe.sub.2 H           CH.sub.2 CHMe.sub.2                                                                      H                                           ______________________________________                                    

                  TABLE 10                                                        ______________________________________                                         ##STR28##                                                                    ______________________________________                                        T = O, W is a single bond, R.sup.2 = Me                                       R.sup.1            R.sup.1                                                    ______________________________________                                        Me                 CH(Me)CH.sub.2 Cl                                          CH.sub.2 F         C(Me)CHBr                                                  CH.sub.2 Cl        CHCHMe                                                     CH.sub.2 Br        CH(Me)SMe                                                  CHF.sub.2          CH(Me)OMe                                                  CHCl.sub.2         (CH.sub.2).sub.3 Me                                        CF.sub.3           CH(Me)CH.sub.2 Me                                          Et                 CH.sub.2 CHMe.sub.2                                        CH.sub.2 CF.sub.3  CMe.sub.3                                                  CH.sub.2 CH.sub.2 F                                                                              cyclobutyl                                                 CH.sub.2 CH.sub.2 Cl                                                                             1-Me-cyclopropyl                                           CH.sub.2 CH.sub.2 Br                                                                             2-Me-cyclopropyl                                           CHFMe              CH.sub.2 -cyclopropyl                                      CHClMe             CH.sub.2 C(Me)CH.sub.2                                     CHBrMe             CHCMe.sub.2                                                CH.sub.2 CHF.sub.2 CHBrCHMe.sub.2                                             CCl.sub.2 Me       CHC(CH.sub.2 Cl).sub.2                                     CH.sub.2 OMe       C(Me).sub.2 CH.sub.2 Cl                                    CH.sub.2 SMe       C(Me).sub.2 OMe                                            CH.sub.2 CF.sub.3  C(Me).sub.2 SMe                                            (CH.sub.2).sub.2 Me                                                                              (CH.sub.2).sub.4 Me                                        CHMe.sub.2         CH(CH.sub.2 CH.sub.3).sub.2                                cyclopropyl        Ph                                                         C(Me)CH.sub.2      CMe.sub.2 Br                                               ______________________________________                                        T = O, R.sup.2 = Me                                                           W          R.sup.1     W          R.sup.1                                     ______________________________________                                        O          Me          S          CH.sub.2 CHMe.sub.2                         O          Et          NH         Me                                          O          nPr         NH         Et                                          O          nBu         NH         nPr                                         O          CHMe.sub.2  NH         nBu                                         O          CH.sub.2 CHCH.sub.2                                                                       NH         CHMe.sub.2                                  O          CH.sub.2 CHMe.sub.2                                                                       NH         CH.sub.2 CHMe.sub.2                         S          Me          NMe        Me                                          S          Et          NMe        Et                                          S          nPr         NMe        nPr                                         S          CHMe.sub.2  NOMe       Me                                          ______________________________________                                        T = S, W is a single bond                                                     R.sup.1    R.sup.2     R.sup.1    R.sup.2                                     ______________________________________                                        Me         Me          CHMe.sub.2 Cl                                          Et         Me          CH.sub.2 CHMe.sub.2                                                                      Br                                          nPr        Me          cyclopropyl                                                                              Et                                          CF.sub.3   Me          CHMe.sub.2 OMe                                         CHMe.sub.2 Me          CH.sub.2 CHMe.sub.2                                                                      OEt                                         CH.sub.2 CHMe.sub.2                                                                      Me          CHMe.sub.2 CN                                          CMe.sub.3  Me          CMe.sub.3  NO.sub.2                                    cyclopropyl                                                                              Me          CMe.sub..sub.3                                                                           NHMe                                        cyclobutyl Me          CMe.sub.3  NMe.sub.2                                   Ph         Me          cyclopropyl                                                                              Br                                          CH.sub.2 CF.sub.3                                                                        Me          CMe.sub.3  Et                                          CHCMe.sub.2                                                                              Me          CH.sub.2 CHMe.sub.2                                                                      CN                                          1-Me-cyclopropyl                                                                         Me          CHMe.sub.2 NEt.sub.2                                   CHMe.sub.2 H           CH.sub.2 CHMe.sub.2                                                                      H                                           ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                         ##STR29##                                                                    WR.sup.1     R.sup.2 WR.sup.1      R.sup.2                                    ______________________________________                                        Me           H       Me            Br                                         Et           H       Et            Br                                         nPr          H       nPr           Br                                         CHMe.sub.2   H       CHMe.sub.2    Br                                         cyclopropyl  H       cyclopropyl   Br                                         cyclobutyl   H       cyclobutyl    Br                                         1-Me-cyclopropyl                                                                           H       1-Me-cyclopropyl                                                                            Br                                         2-Me-cyclopropyl                                                                           H       2-Me-cyclopropyl                                                                            Br                                         CMe.sub.3    H       CMe.sub.3     Br                                         CF.sub.3     H       CF.sub.3      Br                                         CH.sub.2 CF.sub.3                                                                          H       CH.sub.2 CF.sub.3                                                                           Br                                         CHF.sub.2    H       CHF.sub.2     Br                                         C(Me)CH.sub.2                                                                              H       C(Me)CH.sub.2 Br                                         CH.sub.2 OMe H       OCHMe.sub.2   Br                                         CHMe.sub.2   Cl      CHMe.sub.2    NO.sub.2                                   CH.sub.2 CHMe.sub.2                                                                        Cl      CH.sub.2 CHMe.sub.2                                                                         NO.sub.2                                   cyclopropyl  Cl      cyclopropyl   NO.sub.2                                   CMe.sub.3    Cl      CMe.sub.3     NO.sub.2                                   CF.sub.3     Cl      CF.sub.3      NO.sub.2                                   OCHMe.sub.2  Cl      OCHMe.sub.2   NO.sub.2                                   CHMe.sub.2   Et      cyclopropyl   CN                                         CH.sub.2 CHMe.sub.2                                                                        Et      CMe.sub.2     CN                                         OCHMe.sub.2  Et      Me            CN                                         cyclopropyl  Et      cyclobutyl    CN                                         CMe.sub.3    Et      CHMe.sub.2    CN                                         Me           Et      CH.sub.2 CHMe.sub.2                                                                         CN                                         CMe.sub.3    OMe     CMe.sub.3     NHMe                                       Me           OMe     Et            NHMe                                       CHMe.sub.2   OMe     CHMe.sub.2    NMe.sub.2                                  CH.sub.2 CHMe.sub.2                                                                        OMe     CH.sub.2 CHMe.sub.2                                                                         NMe.sub.2                                  cyclopropyl  OMe     cyclopropyl   NHEt                                       OCHMe.sub.2  OMe     CHMe.sub.2    SMe                                        CH.sub.2 CF.sub.3                                                                          OEt     CH.sub.2 CHMe.sub.2                                                                         SEt                                        CHMe.sub.2   OEt     cyclopropyl   CH.sub.2 OMe                               CH.sub.2 CHMe.sub.2                                                                        NEt.sub.2                                                                             CHMe.sub.2    CH.sub.2 SMe                               SCHMe.sub.2  Et      CH.sub.2 CF.sub.3                                                                           OMe                                        NMe.sub.2    Et      SMe           NO.sub.2                                   CH.sub.2 OMe Et      OCHMe.sub.2   NMe.sub.2                                  C(Me)CH      CN      C(Me)CH       CH.sub.2 OMe                               CH.sub.2 OMe Br      NMe.sub.2     CH.sub.2 SMe                               ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                         ##STR30##                                                                    WR.sup.1     R.sup.2 WR.sup.1      R.sup.2                                    ______________________________________                                        Me           H       Me            Br                                         Et           H       Et            Br                                         nPr          H       nPr           Br                                         CHMe.sub.2   H       CHMe.sub.2    Br                                         cyclopropyl  H       cyclopropyl   Br                                         cyclobutyl   H       cyclobutyl    Br                                         1-Me-cyclopropyl                                                                           H       1-Me-cyclopropyl                                                                            Br                                         2-Me-cyclopropyl                                                                           H       2-Me-cyclopropyl                                                                            Br                                         CMe.sub.3    H       CMe.sub.3     Br                                         CF.sub.3     H       CF.sub.3      Br                                         CH.sub.2 CF.sub.3                                                                          H       CH.sub.2 CF.sub.3                                                                           Br                                         CHF.sub.2    H       CHF.sub.2     Br                                         C(Me)CH.sub.2                                                                              H       C(Me)CH.sub.2 Br                                         CH.sub.2 OMe H       OCHMe.sub.2   Br                                         CHMe.sub.2   Cl      CHMe.sub.2    NO.sub.2                                   CH.sub.2 CHMe.sub.2                                                                        Cl      CH.sub.2 CHMe.sub.2                                                                         NO.sub.2                                   cyclopropyl  Cl      cyclopropyl   NO.sub.2                                   CMe.sub.3    Cl      CMe.sub.3     NO.sub.2                                   CF.sub.3     Cl      CF.sub.3      NO.sub.2                                   OCHMe.sub.2  Cl      OCHMe.sub.2   NO.sub.2                                   CHMe.sub.2   Et      cyclopropyl   CN                                         CH.sub.2 CHMe.sub.2                                                                        Et      CMe.sub.2     CN                                         OCHMe.sub.2  Et      Me            CN                                         cyclopropyl  Et      cyclobutyl    CN                                         CMe.sub.3    Et      CHMe.sub.2    CN                                         Me           Et      CH.sub.2 CHMe.sub.2                                                                         CN                                         CMe.sub.3    OMe     CMe.sub.3     NHMe                                       Me           OMe     Et            NHMe                                       CHMe.sub.2   OMe     CHMe.sub.2    NMe.sub.2                                  CH.sub.2 CHMe.sub.2                                                                        OMe     CH.sub.2 CHMe.sub.2                                                                         NMe.sub.2                                  cyclopropyl  OMe     cyclopropyl   NHEt                                       OCHMe.sub.2  OMe     CHMe.sub.2    SMe                                        CH.sub.2 CF.sub.3                                                                          OEt     CH.sub.2 CHMe.sub.2                                                                         SEt                                        CHMe.sub.2   OEt     cyclopropyl   CH.sub.2 OMe                               CH.sub.2 CHMe.sub.2                                                                        NEt.sub.2                                                                             CHMe.sub.2    CH.sub.2 SMe                               SCHMe.sub.2  Et      CH.sub.2 CF.sub.3                                                                           OMe                                        NMe.sub.2    Et      SMe           NO.sub.2                                   CH.sub.2 OMe Et      OCHMe.sub.2   NMe.sub.2                                  C(Me)CH      CN      C(Me)CH       CH.sub.2 OMe                               CH.sub.2 OMe Br      NMe.sub.2     CH.sub.2 SMe                               ______________________________________                                    

                  TABLE 13                                                        ______________________________________                                         ##STR31##                                                                    T    R.sup.2  WR.sup.1    T    R.sup.2                                                                             WR.sup.1                                 ______________________________________                                        O    Me       CMe.sub.3   O    Me    SCHMe.sub.2                              O    Me       Me          O    Me    NMe.sub.2                                O    Me       CHMe.sub.2  O    Me    CF.sub.3                                 O    Me       CH.sub.2 CHMe.sub.2                                                                       O    Br    CHMe.sub.2                               O    Me       cyclopropyl O    Cl    CH.sub.2 CHMe.sub.2                      O    Me       OCHMe.sub.2 O    Et    cyclopropyl                              S    Me       CH.sub.2 CHMe.sub.2                                                                       O    CN    CHMe.sub.2                               O    NMe.sub.2                                                                              CHMe.sub.2  O    NO.sub.2                                                                            CH.sub.2 CHMe.sub.2                      ______________________________________                                    

                  TABLE 14                                                        ______________________________________                                         ##STR32##                                                                    T    R.sup.2  WR.sup.1    T    R.sup.2                                                                             WR.sup.1                                 ______________________________________                                        O    Me       CMe.sub.3   O    Me    SCHMe.sub.2                              O    Me       Me          O    Me    NMe.sub.2                                O    Me       CHMe.sub.2  O    Me    CF.sub.3                                 O    Me       CH.sub.2 CHMe.sub.2                                                                       O    Br    CHMe.sub.2                               O    Me       cyclopropyl O    Cl    CH.sub.2 CHMe.sub.2                      O    Me       OCHMe.sub.2 O    Et    cyclopropyl                              S    Me       CH.sub.2 CHMe.sub.2                                                                       O    CN    CHMe.sub.2                               O    NMe.sub.2                                                                              CHMe.sub.2  O    NO.sub.2                                                                            CH.sub.2 CHMe.sub.2                      ______________________________________                                    

Formulation/Utility

Compounds of this invention will generally be used as a formulation orcomposition with an agriculturally suitable carrier comprising at leastone of a liquid diluent, a solid diluent or a surfactant. Theformulation or composition ingredients are selected to be consistentwith the physical properties of the active ingredient, mode ofapplication and environmental factors such as soil type, moisture andtemperature. Useful formulations include liquids such as solutions(including emulsifiable concentrates), suspensions, emulsions (includingmicroemulsions and/or suspoemulsions) and the like which optionally canbe thickened into gels. Useful formulations further include solids suchas dusts, powders, granules, pellets, tablets, films, and the like whichcan be water-dispersible ("wettable") or water-soluble. Activeingredient can be (micro)encapsulated and further formed into asuspension or solid formulation; alternatively the entire formulation ofactive ingredient can be encapsulated (or "overcoated"). Encapsulationcan control or delay release of the active ingredient. Sprayableformulations can be extended in suitable media and used at spray volumesfrom about one to several hundred liters per hectare. High-strengthcompositions are primarily used as intermediates for furtherformulation.

The formulations will typically contain effective amounts of activeingredient, diluent and surfactant within the following approximateranges which add up to 100 percent by weight.

    ______________________________________                                                     Weight Percent                                                                Active                                                                        Ingredient                                                                            Diluent   Surfactant                                     ______________________________________                                        Water-Dispersible and                                                                        5-90       0-94     1-15                                       Water-soluble Granules,                                                       Tablets and Powders.                                                          Suspensions, Emulsions,                                                                      5-50      40-95     0-15                                       Solutions (including                                                          Emulsifiable Concentrates)                                                    Dusts          1-25      70-99     0-5                                        Granules and Pellets                                                                         0.01-99      5-99.99                                                                              0-15                                       High Strength  90-99      0-10     0-2                                        Compositions                                                                  ______________________________________                                    

Typical solid diluents are described in Watkins, et al., Handbook ofInsecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books,Caldwell, N.J. Typical liquid diluents are described in Marsden,Solvents Guide, 2nd Ed., Interscience, N.Y., 1950. McCutcheon'sDetergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, N.J.,as well as Sisely and Wood, Encyclopedia of Surface Active Agents,Chemical Publ. Co., Inc., New York, 1964, list surfactants andrecommended uses. All formulations can contain minor amounts ofadditives to reduce foam, caking, corrosion, microbiological growth andthe like, or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohols,polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acidesters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzenesulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates,naphthalene sulfonate formaldehyde condensates, polycarboxylates, andpolyoxyethylene/polyoxypropylene block copolymers. Solid diluentsinclude, for example, clays such as bentonite, montmorillinite,attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth,urea, calcium carbonate, sodium carbonate and bicarbonate, and sodiumsulfate. Liquid diluents include, for example, water,N,N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethyleneglycol, polypropylene glycol, paraffins, alkylbenzenes,alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn,peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters,ketones such as cyclohexanone, 2-heptanone, isophorone and4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol,cyclohexanol, decanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared bysimply mixing the ingredients. Dusts and powders can be prepared byblending and, usually, grinding as in a hammer mill or fluid-energymill. Suspensions are usually prepared by wet-milling; see, for example,U.S. Pat. No. 3,060,084. Granules and pellets can be prepared byspraying the active material upon preformed granular carriers or byagglomeration techniques. See Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp 147-48, Perry's Chemical Engineer'sHandbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 andfollowing, and WO 91/13546. Pellets can be prepared as described in U.S.Pat. No. 4,172,714. Water-dispersible and water-soluble granules can beprepared as taught in U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442and DE 3,246,493. Tablets can be prepared as taught in U.S. Pat. No.5,180,587, U.S. Pat. No. 5,232,701 and U.S. Pat. No. 5,208,030. Filmscan be prepared as taught in GB 2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see U.S. Pat.No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples10-41; U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col. 7, line 62and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166,167 and 169-182; U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col.5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, JohnWiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., WeedControl Handbook, 8th Ed., Blackwell Scientific Publications, Oxford,1989.

In the following Examples, all percentages are by weight and allformulations are prepared in conventional ways. Compound numbers referto compounds in Index Tables A-C.

    ______________________________________                                        Example A                                                                     High Strength Concentrate                                                     Compound 3              98.5%                                                 silica aerogel          0.5%                                                  synthetic amorphous fine silica                                                                       1.0%.                                                 Example B                                                                     Wettable Powder                                                               Compound 11             65.0%                                                 dodecylphenol polyethylene glycol ether                                                               2.0%                                                  sodium ligninsulfonate  4.0%                                                  sodium silicoaluminate  6.0%                                                  montmorillonite (calcined)                                                                            23.0%.                                                Example C                                                                     Granule                                                                       Compound 3              10.0%                                                 attapulgite granules (low volatile matter,                                                            90.0%.                                                0.71/0.30 mm; U.S.S. No. 25-50 sieves)                                        Example D                                                                     Extruded Pellet                                                               Compound 11             25.0%                                                 anhydrous sodium sulfate                                                                              10.0%                                                 crude calcium ligninsulfonate                                                                         5.0%                                                  sodium alkylnaphthalenesulfonate                                                                      1.0%                                                  calcium/magnesium bentonite                                                                           59.0%.                                                ______________________________________                                    

Tests results indicate that the compounds of the present invention arehighly active preemergent and/or postemergent herbicides and/or plantgrowth regulants. Many of them have utility for broad-spectrum pre-and/or postemergence weed control in areas where complete control of allvegetation is desired such as around fuel storage tanks, industrialstorage areas, parking lots, drive-in theaters, around billboards andhighway and railroad structures. Some of the compounds are useful forthe control of selected grass and broadleaf weeds with tolerance toimportant agronomic crops which include but are not limited to barley,cotton, wheat, rape, sugarbeets, corn, soybeans, rice, and plantationcrops including coffee, cocoa, oil palm, rubber, sugarcane, citrus,grapes, fruit trees, nut trees, banana, plantain, pineapple, conifers,e.g., loblolly pine, and turf species, e.g., Kentucky bluegrass, St.Augustine grass, Kentucky fescue and bermudagrass. Those skilled in theart will appreciate that not all compounds are equally effective againstall weeds. Alternatively, the subject compounds are useful to modifyplant growth.

Compounds of this invention can be used alone or in combination withother commercial herbicides, insecticides or fungicides. A mixture ofone or more of the following herbicides with a compound of thisinvention may be particularly useful for weed control: acetochlor,acifluorfen and its sodium salt, acrolein (2-propenal), alachlor,ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam,atrazine, azimsulfuron, benazolin, benazolin-ethyl, benfluralin,benfuresate, bensulfuron-methyl, bensulide, bentazone, bifenox,bromacil, bromoxynil, bromoxynil octanoate, butachlor, butralin,butylate, chlomethoxyfen, chloramben, chlorbromuron, chloridazon,chlorimuron-ethyl, chlomitrofen, chlorotoluron, chlorpropham,chlorsulfuron, chlorthal-dimethyl, cinmethylin, cinosulfuron, clethodim,clomazone, clopyralid, clopyralid-olamine, cyanazine, cycloate,cyclosulfamuron, 2,4-D and its butotyl, butyl, isoctyl and isopropylesters and its dimethylammonium, diolamine and trolamine salts,daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and itsdimethylammonium, potassium and sodium salts, desmedipham, desmetryn,dicamba and its dimethylammonium, potassium and sodium salts,dichlobenil, dichlorprop, diclofop-methyl, difenzoquat metilsulfate,diflufenican, dimepiperate, dimethylarsinic acid and its sodium salt,dinitramine, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC,endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl,ethofumesate, ethylα,2-dichloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl]-4-fluorobenzenepropanoate(F8426), fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenuron, fenuron-TCA,flareprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl,flazasulfuron, fluazifop-butyl, fluazifop-P-butyl, fluchloralin,flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron,fluoroglycofen-ethyl, flupoxam, fluridone, flurochloridone, fluroxypyr,fomesafen, fosamine-ammonium, glufosinate, glufosinate-ammonium,glyphosate, glyphosate-isopropylammonium, glyphosate-sesquisodium,glyphosate-trimesium, halosulfuron-methyl, haloxyfop-etotyl,haloxyfop-methyl, hexazinone, imazamethabenz-methyl, imazapyr,imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium,imazosulfuron, ioxynil, ioxynil octanoate, ioxynil-sodium, isoproturon,isouron, isoxaben, lactofen, lenacil, linuron, maleic hydrazide, MCPAand its dimethylammonium, potassium and sodium salts, MCPA-isoctyl,mecoprop, mecoprop-P, mefenacet, mefluidide, metam-sodium,methabenzthiazuron, methyl [[2-chloro-4-fluoro-5-[(tetrahydro-3-oxo-1H,3H-[1,3,4]thiadiazolo[3,4-α]pyridazin-1-ylidene)amino]phenyl]thioacetate(KIH 9201), methylarsonic acid and its calcium, monoammonium, monosodiumand disodium salts, methyl[[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyethylidene]amino]oxy]acetate(AKH-7088), methyl 5-[[[[(4,6-dimethyl-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-1-(2-pyridinyl)-1H-pyrazole-4-carboxylate(NC-330), metobenzuron, metolachlor, metoxuron, metribuzin,metsulfuron-methyl, molinate, monolinuron, napropamide, naptalarn,neburon, nicosulfuron, norflurazon, oryzalin, oxadiazon, oxyfluorfen,paraquat dichloride, pebulate, pendimethalin, perfluidone, phenmedipham,picloram, picloram-potassium, pretilachlor, primisulfuron-methyl,prometon, prometryn, propachlor, propanil, propazine, propham,propyzamide, prosulfuron, pyrazolynate, pyrazosulfuron-ethyl,quinclorac, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl,rimsulfuron, sethoxydim, siduron, simazine, sulcotrione (ICIA0051),sulfentrazone, sulfometuron-methyl, TCA, TCA-sodium, tebuthiuron,terbacil, terbuthylazine, terbutryn, thenylchlor, thifensulfuron-methyl,thiobencarb, tralkoxydim, tri-allate, triasulfuron, tribenuron-methyl,triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane,trifluralin, triflusulfuron-methyl, and vernolate.

In certain instances, combinations with other herbicides having asimilar spectrum of control but a different mode of action will beparticularly advantageous for preventing the development of resistantweeds.

A herbicidally effective amount of the compounds of this invention isdetermined by a number of factors. These factors include: formulationselected, method of application, amount and type of vegetation present,growing conditions, etc. In general, a herbicidally effective amount ofa compound(s) of this invention is 0.001 to 20 kg/ha with a preferredrange of 0.004 to 1.0 kg/ha. One skilled in the art can easily determinethe herbicidally effective amount necessary for the desired level ofweed control.

The following Tests demonstrate the control efficacy of the compounds ofthis invention against specific weeds. The weed control afforded by thecompounds is not limited, however, to these species. See Index TablesA-C for compound descriptions.

                  INDEX TABLE A                                                   ______________________________________                                         ##STR33##                                                                    Cmpd No.                                                                              T     W      R.sup.1     R.sup.2                                                                            m   mp (°C.)                     ______________________________________                                        1       O     bond   CH.sub.3    CH.sub.3                                                                           1   113-115                             2 (Ex. 4)                                                                             O     bond   C(CH.sub.3).sub.3                                                                         CH.sub.3                                                                           1   89-90                               3       O     bond   CH(CH.sub.3).sub.2                                                                        CH.sub.3                                                                           1   143-144                             4       O     bond   CH.sub.2 CH(CH.sub.3).sub.2                                                               CH.sub.3                                                                           1   104-105                             5       O     O      CH(CH.sub.3).sub.2                                                                        CH.sub.3                                                                           1   92-93                               6 (Ex. 3)                                                                             O     bond   cyclopropyl CH.sub.3                                                                           1   138-139                             7       O     bond   1-CH.sub.3 -cyclopropyl                                                                   CH.sub.3                                                                           1   81-82                               8       O     bond   CF.sub.3    CH.sub.3                                                                           1   82-83                               ______________________________________                                    

                                      INDEX TABLE B                               __________________________________________________________________________     ##STR34##                                                                    Cmpd No.                                                                            X  Y    Z    R.sup.3                                                                           R.sup.4                                                                         R.sup.5                                                                            m mp (°C.)                               __________________________________________________________________________    9     CH N    COCHF.sub.2                                                                        CH.sub.3                                                                          H H    1 106-107                                       10    CH N(O) CH   CH.sub.3                                                                          H OCHF.sub.2                                                                         1 120-121                                       11 (Ex. 1)                                                                          CH N    CH   CH.sub.3                                                                          H OCHF.sub.2                                                                         1 154-155                                       __________________________________________________________________________

                  INDEX TABLE C                                                   ______________________________________                                         ##STR35##                                                                    Cmpd No. T      W       R.sup.1                                                                             R.sup.2                                                                             m   mp (°C.)                       ______________________________________                                        12 (Ex. 2)                                                                             O      bond    CH.sub.3                                                                            CH.sub.3                                                                            1   105-107                               ______________________________________                                    

TEST A

Seeds of barley (Hordeum vulgare), barnyardgrass (Echinochloacrus-galli), bedstraw (Galium aparine), blackgrass (Alopecurusmyosuroides), chickweed (Stellaria media), cocklebur (Xanthiumpensylvanicum), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass(Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail(Setaria faberii), lambsquarters (Chenopodium album), morningglory(Ipomoea hederacea), rape (Brassica napus), rice (Oryza saliva), sorghum(Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulgaris),velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wildbuckwheat (Polygonurn convolvulus), wild oat (Avena fatua) and purplenutsedge (Cyperus rotundus) tubers were planted and treated preemergencewith test chemicals formulated in a non-phytotoxic solvent mixture whichincludes a surfactant.

At the same time, these crop and weed species were also treated withpostemergence applications of test chemicals formulated in the samemanner. Plants ranged in height from two to eighteen cm (one to fourleaf stage) for postemergence treatments. Treated plants and controlswere maintained in a greenhouse for twelve to sixteen days, after whichall species were compared to controls and visually evaluated. Plantresponse ratings, summarized in Table A, are based on a scale of 0 to 10where 0 is no effect and 10 is complete control. A dash (-) responsemeans no test result.

                  TABLE A                                                         ______________________________________                                        Rate 1000                                                                              COMPOUND    Rate 1000  COMPOUND                                      g/ha     1     2     3   4   g/ha     1   2   3   4                           ______________________________________                                        POSTEMERGENCE    PREEMERGENCE                                                 Barley   4     1     8   5   Barley   3   0   5   3                           Barnyard-                                                                              9     2     9   9   Barnyard-                                                                              9   4   9   10                          grass                        grass                                            Bedstraw 2     6     9   9   Bedstraw 0   0   8   9                           Blackgrass                                                                             5     2     9   8   Blackgrass                                                                             5   1   10  10                          Chickweed                                                                              3     3     8   7   Chickweed                                                                              9   0   9   8                           Cocklebur                                                                              2     7     7   6   Cocklebur                                                                              0   0   0   0                           Corn     8     2     8   6   Corn     3   0   6   5                           Cotton   1     3     8   10  Cotton   0   0   1   9                           Crabgrass                                                                              9     2     10  9   Crabgrass                                                                              10  10  10  10                          Downy    1     1     9   2   Downy    5   1   10  8                           brome                        brome                                            Giant foxtail                                                                          9     1     9   9   Giant foxtail                                                                          9   9   10  10                          Lambsquarter                                                                           8     6     9   9   Lambsquarter                                                                           9   8   9   10                          Morningglory                                                                           5     8     9   10  Morningglory                                                                           5   1   8   10                          Nutsedge 1     0     3   3   Nutsedge 3   0   3   3                           Rape     1     3     6   8   Rape     3   0   6   9                           Rice     2     2     7   3   Rice     1   0   3   3                           Sorghum  7     2     7   5   Sorghum  3   1   5   3                           Soybean  5     5     7   9   Soybean  3   0   6   6                           Sugar beet                                                                             7     7     10  10  Sugar beet                                                                             6   2   10  10                          Velvetleaf                                                                             9     2     9   8   Velvetleaf                                                                             6   1   10  10                          Wheat    1     2     8   3   Wheat    1   0   7   6                           Wild buck-                                                                             6     3     9   9   Wild buck-                                                                             2   0   2   7                           wheat                        wheat                                            Wild oat 5     1     9   8   Wild oat 9   5   10  10                          ______________________________________                                               COMPOUND             COMPOUND                                          Rate 400 g/ha                                                                          9       10      Rate 400 g/ha                                                                          9     10                                    ______________________________________                                        POSTEMERGENCE    PREEMERGENCE                                                 Barley   6       3       Barley   8     1                                     Barnyard-                                                                              5       2       Barnyard-                                                                              10    3                                     grass                    grass                                                Bedstraw 9       7       Bedstraw 9     7                                     Blackgrass                                                                             4       2       Blackgrass                                                                             9     1                                     Chickweed                                                                              8       6       Chickweed                                                                              9     8                                     Cocklebur                                                                              8       4       Cocklebur                                                                              1     0                                     Corn     3       2       Corn     4     1                                     Cotton   9       9       Cotton   3     3                                     Crabgrass                                                                              9       10      Crabgrass                                                                              10    9                                     Downy    3       1       Downy    9     1                                     brome                    brome                                                Giant foxtail                                                                          6       2       Giant foxtail                                                                          10    6                                     Lambsquarter                                                                           9       9       Lambsquarter                                                                           9     9                                     Morningglory                                                                           9       8       Morningglory                                                                           5     3                                     Nutsedge 1       0       Nutsedge 4     0                                     Rape     9       6       Rape     8     7                                     Rice     3       2       Rice     3     0                                     Sorghum  3       1       Sorghum  3     0                                     Soybean  6       6       Soybean  1     1                                     Sugar beet                                                                             9       9       Sugar beet                                                                             10    10                                    Velvetleaf                                                                             6       2       Velvetleaf                                                                             8     6                                     Wheat    3       2       Wheat    8     0                                     Wild buck-                                                                             7       4       Wild buck-                                                                             8     3                                     wheat                    wheat                                                Wild oat 5       2       Wild oat 9                                           ______________________________________                                               COMPOUND             COMPOUND                                          Rate 200 g/ha                                                                          1     2     3   4   Rate 200 g/ha                                                                          1   2   3   4                           ______________________________________                                        POSTEMERGENCE    PREEMERGENCE                                                 Barley   1     1     6   2   Barley   0   0   1   1                           Barnyard-                                                                              4     1     8   7   Barnyard-                                                                              3   0   7   6                           grass                        grass                                            Bedstraw 2     3     7   7   Bedstraw 0   0   2   4                           Blackgrass                                                                             1     1     6   2   Blackgrass                                                                             2   0   3   2                           Chickweed                                                                              3     2     7   5   Chickweed                                                                              2   0   6   4                           Cocklebur                                                                              2     3     5   2   Cocklebur                                                                              0   0   0   0                           Corn     2     1     6   5   Corn     1   0   4   5                           Cotton   1     2     4   9   Cotton   0   0   0   0                           Crabgrass                                                                              4     0     10  7   Crabgrass                                                                              8   1   10  10                          Downy    1     0     3   1   Downy    1   0   2   2                           brome                        brome                                            Giant foxtail                                                                          4     1     9   6   Giant foxtail                                                                          7   1   9   9                           Lambsquarter                                                                           6     2     9   9   Lambsquarter                                                                           0   0   9   9                           Morningglory                                                                           3     7     9   10  Morningglory                                                                           1   0   3   3                           Nutsedge 1     0     1   3   Nutsedge 0   0   0   3                           Rape     0     2     2   6   Rape     0   0   1   9                           Rice     0     0     4   2   Rice     0   0   1   1                           Sorghum  0     0     3   1   Sorghum  0   0   2   1                           Soybean  3     4     6   8   Soybean  0   0   2   3                           Sugar beet                                                                             2     2     9   8   Sugar beet                                                                             3   0   10  10                          Velvetleaf                                                                             6     1     7   6   Velvetleaf                                                                             1   0   10  10                          Wheat    1     1     2   3   Wheat    0   0   2   1                           Wild buck-                                                                             1     1     6   4   Wild buck-                                                                             0   0   2   3                           wheat                        wheat                                            Wild oat 1     0     4   1   Wild oat 2   0   9   7                           ______________________________________                                               COMPOUND             COMPOUND                                          Rate 100 g/ha                                                                          9       10      Rate 100 g/ha                                                                          9     10                                    ______________________________________                                        POSTEMERGENCE    PREEMERGENCE                                                 Barley   3       3       Barley   0     0                                     Barnyard-                                                                              3       1       Barnyard-                                                                              1     1                                     grass                    grass                                                Bedstraw 7       3       Bedstraw 1     1                                     Blackgrass                                                                             2       2       Blackgrass                                                                             1     0                                     Chickweed                                                                              4       3       Chickweed                                                                              3     5                                     Cocklebur                                                                              7       3       Cocklebur                                                                              0     0                                     Corn     2       1       Corn     1     0                                     Cotton   9       9       Cotton   0     0                                     Crabgrass                                                                              7       9       Crabgrass                                                                              9     2                                     Downy    1       1       Downy    2     0                                     brome                    brome                                                Giant foxtail                                                                          2       1       Giant foxtail                                                                          8     1                                     Lambsquarter                                                                           8       9       Lambsquarter                                                                           6     8                                     Morningglory                                                                           9       1       Morningglory                                                                           0     2                                     Nutsedge 0       0       Nutsedge 0     0                                     Rape     7       8       Rape     1     3                                     Rice     3       1       Rice     0     0                                     Sorghum  2       1       Sorghum  0     0                                     Soybean  4       4       Soybean  0     0                                     Sugar beet                                                                             9       9       Sugar beet                                                                             2     6                                     Velvetleaf                                                                             3       1       Velvetleaf                                                                             1     1                                     Wheat    2       2       Wheat    1     0                                     Wild buck-                                                                             5       2       Wild buck-                                                                             1     0                                     wheat                    wheat                                                Wild oat 2       2       Wild oat 6     1                                     ______________________________________                                    

What is claimed is:
 1. A compound selected from Formula I, an N-oxideand an agriculturally-suitable salt thereof, ##STR36## wherein: Q is##STR37## T is O or S; W is a single bond, O, S or NR⁶ ;X is N or CH; Yis N or CH; Z is N or CR⁷ provided that when Z is CR⁷, then Y is N; R¹is C₁ -C₅ alkyl optionally substituted with C₁ -C₂ alkoxy, OH, 1-3halogens, or C₁ -C₂ alkylthio; CH₂ (C₃ -C₄ cycloalkyl); C₃ -C₄cycloalkyl optionally substituted with 1-3 methyl groups; C₂ -C₄alkenyl; C₂ -C₄ haloalkenyl; or phenyl optionally substituted withhalogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy, nitro or cyano; R² is H, chlorine, bromine, C₁ -C₂ alkyl, C₁-C₂ alkoxy, C₁ -C₂ alkylthio, C₂ -C₃ alkoxyalkyl, C₂ -C₃ alkylthioalkyl,cyano, nitro, NH(C₁ -C₂ alkyl) or N(C₁ -C₂ alkyl)₂ ; R³ is C₁ -C₄ alkyl,C₂ -C₄ alkoxyalkyl, C₂ -C₄ alkenyl, C₂ -C₄ alkynyl, C₁ -C₄ alkoxy, C₁-C₄ alkylthio, C₁ -C₃ alkylamino or N(C₁ -C₃ alkyl)(C₁ -C₃ alkyl); R⁴ isH or F; R⁵ is H, CN, C₁ -C₃ alkyl, C₁ -C₄ haloalkyl, C₃ -C₄halocycloalkyl, C₂ -C₄ haloalkenyl, C₃ -C₄ haloalkynyl, OR⁸, S(O)_(n) R⁹or halogen; R⁶ is H, CH₃ or OCH₃ ; R⁷ is H, CN, C₁ -C₃ alkyl, C₁ -C₄haloalkyl, C₃ -C₄ halocycloalkyl, C₂ -C₄ haloalkenyl, C₃ -C₄haloalkynyl, OR¹⁰, S(O)_(p) R¹¹ or halogen; R⁸ and R¹⁰ are eachindependently C₁ -C₄ alkyl, C3-C₄ alkenyl, C₃ -C₄ alkynyl, C₁ -C₄haloalkyl, C₂ -C₄ haloalkenyl or C₃ -C₄ haloalkynyl; R⁹ and R¹¹ are eachindependently C₁ -C₂ alkyl or C₁ -C₂ haloalkyl; m is 1 or 2; and n and pare each independently 0, 1 or 2;provided that when Z is CR⁷, thenexactly one of R⁵ and R⁷ is H.
 2. A compound of claim 1 wherein:R¹ is C₁-C₄ alkyl optionally substituted with methoxy or 1-3 halogens; C₂ -C₄alkenyl; or C₂ -C₄ haloalkenyl; R² is chlorine, bromine, C₁ -C₂ alkyl,C₁ -C₂ alkoxy, cyano, nitro, NH(C₁ -C₂ alkyl) or N(C₁ -C₂ alkyl)₂ ; andR³ is C₁ -C₃ alkyl, C₂ -C₃ alkoxyalkyl, C₂ -C₃ alkenyl, C₂ -C₃ alkynyl,C₁ -C₂ alkoxy, C₁ -C₂ alkylthio, C₁ -C₂ alkylamino or N(C₁ -C₂ alkyl)(C₁-C₂ alkyl); R⁷ is H, C₁ -C₂ haloalkyl, OR¹⁰, or S(O)_(p) R¹¹ ; R¹⁰ is C₁-C₂ haloalkyl; R¹¹ is C₁ haloalkyl; and p is
 0. 3. A compound of claim 2wherein:T is O; W is a single bond; m is 1; and n is
 0. 4. A compound ofclaim 3 wherein:R⁵ is H, C₁ -C₂ haloalkyl, OR⁸, or SR⁹ ; R⁷ is H, CF₃,or OR¹⁰ ; R⁸ is C₁ -C₂ haloalkyl; R⁹ is C₁ haloalkyl; and R¹⁰ is CF₂ H.5. The compound of claim 4 selected from thegroup:N-[2-(2,2-difluoro-1,3-benzodioxol-4-yl)-4-methylphenyl]-2-methylpropanamide;and8-(2,2-difluoro-1,3-benzodioxol-4-yl)-2-(difluoromethoxy)-6-methylquinoxaline.6. A herbicidal composition comprising a herbicidally effective amountof a compound of claim 1 and at least one of a surfactant, a soliddiluent or a liquid diluent.
 7. A method for controlling the growth ofundesired vegetation comprising contacting the vegetation or itsenvironment with a herbicidally effective amount of a composition ofclaim 6.